Iodine-Catalyzed Synthesis of Chalcogenophenes by the Reaction of 1,3-Dienyl Bromides and Potassium Selenocyanate/Potassium Sulfide (KSeCN/K2S)

Article abstract of DOI:10.1002/adsc.201701232

The methods available for the synthesis of chalcogenophenes, in general, are associated with drawbacks of harsh conditions, use of costly metals, broad applicability, tedious purification process and low yield. To avoid these drawbacks a transition metal-free iodine-catalyzed reaction of aryl-susbstituted 1,3-dienyl bromides with potassium selenocyanate/potassium sulfide (KSeCN/K₂S) leading to the corresponding selenophenes and thiophenes has been developed. Iodine is relatively benign, less expensive and readily available. Several diversely substituted selenophenes and thiophenes have been obtained by this procedure in high yields. Using this procedure 2-(4-chlorophenyl)thiophene, a key intermediate for the synthesis of a melanin concentrating hormone receptor ligand involved in the treatment of eating disorders, weight gain, obesity, depression and anxiety has been synthesized. Although the reaction is one-pot essentially it proceeds in two steps involving a selenocyanate/thiolate intermediate leading to the selenophene/thiophene. The simple operation, use of inexpensive reagents and a metal-free process make this procedure more attractive for an easy access to substituted selenophenes and thiophenes. (Figure presented.).

Full text of DOI:10.1002/adsc.201701232

Title: Iodine Catalyzed Synthesis of Chalcogenophenes by the
Reaction of 1,3-Dienyl Bromides and KSeCN/K2S
Authors: Brindaban Ranu and Pintu Maity
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10.1002/adsc.201701232
Advanced Synthesis & Catalysis
FULL PAPER
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Iodine Catalyzed Synthesis of Chalcogenophenes by the
Reaction of 1,3-Dienyl Bromides and KSeCN/K2S
Pintu Maitya and Brindaban C. Ranua*
a
Department of Organic Chemistry, Indian Association for the Cultivation of Science, Jadavpur, Kolkata – 700032,
India, E-mail: ocbcr@iacs.res.in
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Abstract. The methods available for the synthesis of Using this procedure 2-(4-chlorophenyl)thiophene, a key
chalcogenophenes, in general, are associated with drawbacks intermediate for the synthesis of a melanin concentrating
of harsh conditions, use of costly metals, broad applicability, hormone receptor ligand involved in the treatment of eating
tedious purification process and low yield. To avoid these disorders, weight gain, obesity, depression and anxiety has
drawbacks a transition metal free iodine catalyzed reaction been synthesized. Although the reaction is one-pot
of aryl susbstituted 1,3-dienyl bromides with KSeCN/K2S essentially it proceeds in two steps involving
leading to the corresponding selenophenes and thiophenes selenocyanate/thiolate intermediate leading
a
to
has been developed. Iodine is relatively benign, less selenophene/thiophene. The simple operation, use of
expensive and readily available. Several diversely inexpensive reagent and a metal free process make this
substituted selenophenes and thiophenes have been obtained procedure more attractive for an easy access to substituted
by this procedure in high yields.
selenophenes and thiophenes.
Keywords: selenophene; thiophene; iodine; 1,3-dienyl
bromide; 1,3-dienylselenocyanate
Introduction
Figure 1. Some biologically important chalcogenophene
derivatives.
Chalcogenophenes, particularly selenophene and
thiophene have received intense recent interest as
many of them showed promising biological activities
Thus, development of efficient procedure for the
synthesis of chalcogenophene is of much importance.
Surprisingly the methods for their synthesis are very
limited. The classical procedure involves heating of
including
antitumoral,[1]
anticonvulsant,[2]
among
hepatoprotective,[3]
antihypertensive,[4]
others.[5] In addition, these compounds are versatile
building blocks for the synthesis of many biologically
active compounds and natural products (Figure 1).[6]
hexane-2,5-dione
and
phosphorus
pentaselenide/pentasulfide in a sealed tube at high
temperature.[7] Obviously these procedures suffer
from limitations of harsh conditions, low yields and
tedious purification process. Later, several improved
procedures including electrophlic cyclization of
homopropargyl selenides and subsequent oxidation
by DDQ,[8] copper iodide catalyzed cyclization of
(Z)-selenoenynes to produce selenophenes,[9] and Cu-
catalyzed double S-alkenylation of potassium sulfide
leading to thiophenes,[10] have been reported among
others.[11] In these procedures access to starting
homopropargyl selenides and (Z)-selenoenynes
requires multi-step synthesis and this limits its
applicability to industry. Recently we demonstrated
an efficient procedure for the synthesis of
selenophenes by a simple one-pot reaction of 1,3-
dienyl bromides and KSeCN catalyzed by CuO
nanoparticles.[12] However this is not equally
1
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10.1002/adsc.201701232
Advanced Synthesis & Catalysis
effective for thiophenes. Thus we sought to have a
general and simpler procedure with uniform
applicability to the synthesis of selenophene as well
as thiophene. We report here a transition metal free
iodine catalyzed reaction of 1,3-dienyl bromide and
KSeCN/ K2S respectively towards synthesis of
selenophenes and thiophenes (Scheme 1). Notably,
iodine is relatively benign, less expensive and readily
available.
Entry
Catalyst
Solvent
Temp.
(oC)
90
Time
(h)
8
Yield
(%)[b]
70
1
2
3
4
5
6
7
I2 (20 mol%)
I2 (20 mol%)
I2 (20 mol%)
I2 (20 mol%)
I2 (20 mol%)
DMSO
DMSO
DMSO
DMSO
DMSO
90
10
12
12
12
12
12
77
90
85
80
55
100
90
75
NaI (20 mol%) DMSO
-
PhI(OAc)2 (20
mol%)
DMSO
90
-
8
I2 (20 mol%)
I2 (20 mol%)
I2 (20 mol%)
I2 (20 mol%)
I2 (20 mol%)
I2 (20 mol%)
-
DMF
90
90
90
90
90
90
90
90
90
90
90
12
12
12
12
12
12
12
12
12
12
12
71
52
-
9
NMP
10
11
12
13
14
15
16
17[c]
18[d]
CH3CN
dioxane
xylene
H2O
-
-
-
DMSO
DMSO
DMSO
DMSO
DMSO
-
I2 (30 mol%)
I2 (10 mol%)
I2 (20 mol%)
I2 (20 mol%)
79
65
79
72
[a]
Reaction conditions: A mixture of 1-((1E,3E)-4-
bromobuta-1,3-dien-1-yl)-2-methoxybenzene (1.0 mmol),
KSeCN (1.2 mmol), catalyst (20 mol%), in dry solvent (2.5
mL) was heated under argon for a certain time.
Scheme 1. Synthesis of chalcogenophenes from 1,3-dienyl
bromides
[b] Yield of isolated products.
[c] KSeCN (1.5 mmol).
[d] KSeCN (1.0 mmol).
Results and Discussion
To optimize the reaction conditions, several
experiments for a representative reaction of (1-
((1E,3E)-4-bromobuta-1,3-dien-1-yl)-2-
methoxybenzene and KSeCN with variation of
reaction parameters such as solvent, catalyst,
temperature, and reaction time were performed. The
results are summarized in Table 1. 20 mol% of I2
catalyzed the reaction in DMSO (solvent) at 90 °C for
12 h to provide the best yield (Table 1, entry 3). Use
of iodine derivatives such as sodium iodide (NaI) and
phenyliodoniumdiacetate ( PhI(OAc)2 ) did not
produce the product (Table 1, entries 6 and 7). Other
solvents such as DMF and NMP led to relatively low
yield (Table 1, entries 8 and 9). The reaction did not
occur at all in CH3CN, dioxane, xylene and H2O
(Table 1, entries 10-13). The reaction did not proceed
satisfactorily when they were performed at higher
Thus, in a typical procedure, a mixture of 1,3-dienyl
bromide and KSeCN was heated in DMSO at 90 °C
in the presence of 20 mol% of I2 for a certain period
of time (TLC). The results are summarized in Table 2.
A variety of aryl substituted 1,3-dienyl bromides
underwent selenylation followed by cyclization to
produce the corresponding selenophenes.
Both electron-donating (-OMe) and –withdrawing
group (-NO2 ) substituted ((1E,3E)-4-bromobuta-1,3-
dien-1-yl)benzenes are compatible in this reaction to
afford the corresponding 2-aryl selenophenes (2b, 2e,
2f and 2g).
o
o
o
(100 C) and lower temperature (80 C) than 90 C
(Table 1, entries 4 and 5). The reaction time of 12 h
was found to be the optimum to get the best result
(Table 1, entries 1 and 2). The reaction did not occur
at all in the absence of I2 (Table 1, entry 14). The
higher (30 mol% ) and lower (10 mol%) amount of I2
were not good enough (Table 1, entries 15 and 16).
The reaction produced relatively low yield using 1.5
equivalent and 1.0 equivalent of KSeCN (Table 1,
entries 17 and 18).
Table 2. Iodine catalyzed synthesis of 2-aryl selenophenes
from 1,3-dienyl bromides.[a]
Table 1. Optimization of reaction conditions[a]
2
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10.1002/adsc.201701232
Advanced Synthesis & Catalysis
[a]
Reaction conditions: A mixture of 1,3-dienyl bromide
(1.0 mmol), KSeCN (1.2 mmol), I2 (20 mol%) in dry
DMSO (2.5 mL) was heated under argon for 10-12 h.
[b] Yield of isolated products.
4-((1E,3E)-4-Bromobuta-1,3-dien-1-yl)-2-
methoxyphenyl acetate
smoothly reacted with
KSeCN to produce the corresponding selenophene
product (2h). Reactions with aryl-1,3-dienyl
bromides having aryl, alkyl and halogen substituents
(-Ph, -pentyl, -hexyl and -Cl) on the vinyl carbon
were successful producing the corresponding 2-
phenyl-3-substituted selenophenes (2i, 2j, 2k and 2l)
o
at 110 C. Halogen (-Br, -Cl and –F) substituted
((1E,3E)-4-bromobuta-1,3-dien-1-yl)benzenes also
underwent reaction smoothly to provide the
corresponding selenophene products (2c, 2d and 2n).
The reaction is highly chemoselective as the halogens
(-Br, -Cl and -F) on the aromatic ring remained intact
and these can be used for further functionalization. 9-
((1E,3E)-4-bromobuta-1,3-dien-1-yl)anthracene
reacted with KSeCN to produce 2-(anthracen-9-
yl)selenophene without any difficulty (2m). The
NH2- substituted dienyl bromide also reacted with
KSeCN to afford the corresponding product 2-
(selenophen-2-yl)aniline (2o) with good yield.
Heteroaryl unit such as furan substituted 1,3-dienyl
bromide also participated in this reaction successfully
to
provide
2-(selenophen-2-yl)furan
(2p).
Interestingly 1,3,5- trienyl bromide furnished 2-vinyl
selenophene only (2q) and formation of no selenepine
was observed.
When we tried the synthesis of thiophenes by the
same protocol of the reaction of 4-phenyl-1,3-dienyl
bromide with KSCN, no corresponding product of
thiophene was formed (Table 3, entry 1). We then
performed the reaction using K2S and it was found to
provide the corresponding thiophene. The reaction
condition was optimized (Table 3) to give the best
o
result in DMF at 110 C for 12 hours (Table 3, entry
4).
By this procedure we have synthesized a series of
substituted thiophenes from the reaction of 1,3-dienyl
bromides and K2S in the presence of 20 mol% I2.
Table 3. Standardization of reaction conditions for the
synthesis of 2-aryl thiophenes.[a]
Entry
S-source
Solvent
Temp.
(oC)
90
Time (h) Yield
(%)[b]
1
2
3
4
KSCN
K2S
DMSO
DMSO
DMSO
DMF
12
12
12
12
-
90
45
61
78
K2S
110
110
K2S
3
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10.1002/adsc.201701232
Advanced Synthesis & Catalysis
5
6
5
K2S
K2S
K2S
NMP
DMF
DMF
110
110
110
12
14
10
49
75
69
The results are provided in Table 4. The unsubstituted
((1E,3E)-4-bromobuta-1,3-dien-1-yl)benzene
underwent reaction with K2S to afford 2-phenyl
thiophene (3a). The reaction of both electron-
donating (-OMe) and –withdrawing group (-NO2)
[a]
Reaction conditions:
A mixture of ((1E,3E)-4-
bromobuta-1,3-dien-1-yl)benzene (1.0 mmol), S-source
(1.2 mmol), I2 (20 mol%), in dry solvent (2.5 mL) was
heated under argon for a certain time.
substituted
((1E,3E)-4-bromobuta-1,3-dien-1-
yl)benzenes produced the corresponding 2-aryl
thiophenes (3b, 3d and 3e). Diversely substituted (Ph,
Me, Pentyl, Cl) (1E,3E)-4-bromobuta-1,3-dien-1-
yl)benzenes are compatible in this reaction to afford
the corresponding 2-aryl thiophenes (3f, 3g, 3h and
3j). Halogen (-F, -Cl) substituted 1,3-dienyl bromides
also produced the corresponding products by keeping
the halogens intact (3c and 3f). 9-((1E,3E)-4-
bromobuta-1,3-dien-1-yl) anthracene produced 2-
[b] Yield of isolated products.
Table 4. Iodine catalyzed synthesis of 2-aryl thiophene by
the reaction of 1,3-dienyl bromide and K2S.[a]
(anthracen-9-yl)thiophene
(3i)
under
this
standardized condition. 4-((1E,3E)-4-Bromobuta-1,3-
dien-1-yl)-2-methoxyphenyl acetate provided the
corresponding thiophene product (3k).
Using our procedure, we have synthesized 2-(4-
chlorophenyl)thiophene (3l) which is
a
key
intermediate for the synthesis of a patented melanin
concentrating hormone receptor ligand involved in
the treatment of eating disorders, weight gain, obesity,
depression and anxiety. [6c]
It was observed that the reaction of 1,3-dienyl
bromide with KSeCN at 90 oC (Scheme 2) in
presence of I2 produced 1,3-dienyl selenocyanate
which was further converted to the corresponding
o
selenophene at 110 C (Scheme 3). Thus 1,3-dienyl
selenocyanate is considered to be an intermediate
towards formation of selenophene. The intermediacy
of
selenocyanate
for
the
formation
of
benzoselenophene was also reported earlier.[13] So
basically, the reaction proceeds by two steps
involving selenocyanate formation and selenophene
formation from selenocyanate in the final stage.
When we have performed the first step of
selenocyanate formation in the presence of TEMPO
(Scheme 3, eq. 4) it was found that TEMPO does not
have any effect on the reaction. This indicates that the
formation of selenocyanate is not likely to go by the
radical pathway. Next we have performed two
reactions
using
1-methoxy-2-((1E,3E)-4-
selenocyanatobuta-1,3-dien-1-yl)benzene as starting
material in the presence and in the absence of
TEMPO under the same conditions (Scheme 3, eq.3).
In the absence of TEMPO the corresponding
selenophene was obtained in good yield, whereas the
other reaction in the presence of TEMPO was
completely quenched. These observations established
that the first step of selenocyanate formation was an
ionic process while the second one towards
selenophene was a radical one.
[a]
Reaction conditions: A mixture of 1,3-dienyl bromide
(1.0 mmol), K2S (1.2 mmol), I2 (20 mol%), in dry DMSO
(2.5 mL) was heated under argon for 10-12 h.
[b] Yield of isolated products.
4
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10.1002/adsc.201701232
Advanced Synthesis & Catalysis
Scheme 4. Possible reaction pathway.
Scheme 2. Iodine catalyzed synthesis of 1,3-dienyl
selenocyanate.
Conclusion
In summary, we have demonstrated an efficient
procedure for the synthesis aryl/alkyl substituted
selenophenes and thiophenes by the reaction of
substituted 1,3-dienyl bromides with KSeCN and K2S
respectively in the presence of iodine without using
any metal. Several diversely substituted selenophenes
and thiophenes were obtained in high yields by this
procedure. Although the reaction is one-pot at 110 oC
essentially it proceeds in two steps involving a
selenocyanate/thiolate intermediate leading to
selenophene/thiophene. A possible mechanism has
been suggested. The simple operation, use of
inexpensive reagent and a metal free process make
this procedure more attractive for the access to
substituted selenophenes and thiophenes.
Scheme 3. Controlled experiments for mechanistic
investigations.
Experimental Section
General Information
Based on these observations, a probable reaction
pathway has been outlined for the selenophene
formation (Scheme 4). The 1,3-dienyl bromide reacts
with iodine to form cycloiodinium ion (A) which
Unless otherwise stated, all reagents and solvents were
purchased from commercial suppliers and were used
without further purification. Reactions were monitored by
thin layer chromatography (TLC) analysis on silica gel 60
F254 and visualization was accomplished by irradiation
with short wave UV light at 254 nm or vaniline staining
solution followed by heating. The crude product was
purified by column chromatography on Merck silica gel
–
interacts with SeCN nucleophile to furnish (E)-(4-
bromo-3-iodo-4-selenocyanatobut-1-en-1-yl)benzene
(B). This intermediate produces the corresponding
trans-1,3-dienyl selenocyanate via E2 elimination and
regeneration of I2. In the next step selenocyanate is
homolytically cleaved to afford the 1,3-dienyl
selenium radical (electrophilic nature) which is
trapped by styrenyl double bond to furnish stable five
membered cyclic intermediate C which leads to
selenophene through oxidation and H+ elimination.
We propose that in case of thiophene formation, the
1,3-dienyl bromide reacts with K2S in the presence of
I2 to form potassium trans-1,3-dienyl thiolate which
is subsequently coverted to 2- thiophene following
the same pathway as in Scheme 4.
(60-120 or 100-200 mesh). H and 13C NMR spectra were
1
recorded on Bruker Avance III 500, 400 and 300 MHz
spectrometers in deuterated solvents. H and 13C chemical
1
shifts are reported in ppm (δ) relative to tetramethylsilane
(TMS). High resolution mass spectra were taken using Q-
Tof micro MS system by electron spray ionization (ESI)
technique. IR spectra were recorded on Perkin Elmer 100
FT-IR Infrared Spectrophotometer as neat for liquid
compounds using neat discs and represented as IR (neat).
The wave numbers (n) are reported in cm−1.
Synthesis of 1,3-dienyl bromides from the
corresponding aldehydes [14]
To a solution of the corresponding aldehyde (10 mmol, 1
eq.) and CBr4 (3.98 g, 12 mmol, 1.2 eq.) in dry
dichloromethane (75 mL), triphenyl phosphine ( 5.5 g, 22
5
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10.1002/adsc.201701232
Advanced Synthesis & Catalysis
mmol, 2.1 eq.) was added at 0 oC in small portion
whereupon the solution turned yellow to white under argon
atmosphere. Then the reaction mixture was stirred for 6 h
at room temperature. Dichloromethane was removed under
reduced pressure from the reaction mixture and petroleum
ether (100 mL) was added, which led to white precipitate
(PPh3=O). After filtration and evaporation of the solvent,
the residue was dissolved in petroleum ether (50 mL),
which led to further precipitation of PPh3=O. Filtration and
evaporation of the solvent afforded the crude dibromide
with >90% purity. To the crude dibromide (< 20 mmol, 1
eq.) and Et3N (20 mmol, 2.0 g, 3.8 mL, 2 eq.) in DMF (6
mL), diethyl phosphite ( 40 mmol, 5.5 g, 5.2 mL, 4 eq.)
unknown and their characterization data (1H NMR, 13C
NMR, IR and elemental analysis) were provided below.
The known compounds were identified by comparison of
their spectroscopic and spectrometric data with those
reported earlier.
(c) Representative experimental procedure for the
coupling of ((1E,3E)-4-bromo-2-methylbuta-1,3-dien-1-
yl)benzene and KSeCN leading to a mixture of ((1E,3E)
and ((1Z,3E)-2-methyl-4-selenocyanatobuta-1,3-dien-1-
yl)benzene (Scheme 2):
o
In a 10 mL round bottom flask, a mixture of ((1E,3E)-4-
bromo-2-methylbuta-1,3-dien-1-yl)benzene (223.1 mg, 1
mmol), KSeCN (173.0 mg, 1.2 mmol), and I2 (51.0 mg, 20
was added at 0 C . The reaction mixture was kept at room
temperature for 12 h. The reaction mixture was then
quenched with dilute HCl (HCl : Water = 1: 2, 20 mL).
The product was extracted with diethyl ether (3 X 20 mL)
and the extract was dried over Na2SO4. Evaporation of
solvent and purification of the residue by short column
chromatography over silica gel (n-hexane) furnished the
pure product.
o
mol%) in DMSO (2.5 mL) was heated at 90 C for 12 h
(TLC) in an oil bath. The reaction mixture was then
allowed to cool and was extracted with EtOAc (3x20 mL).
The extract was washed with saturated Na2S2O3 (10 mL)
and water (10 mL). The organic phase was dried (Na2SO4)
and was evaporated to leave the crude product, which was
purified by column chromatography over silica gel
(EtOAc:n-hexane = 10:90) to provide the mixture of
((1E,3E) and ((1Z,3E)-2-methyl-4-selenocyanatobuta-1,3-
dien-1-yl)benzene. Yield: 181 mg (73%); Yellowish
General Procedure
(a) Representative experimental procedure for the
1
coupling of 1-((1E,3E)-4-bromobuta-1,3-dien-1-yl)-2-
gummy liquid; H NMR (300 MHz, CDCl3) δ = 7.44 –
methoxybenzene
and
KSeCN
to
2-(2-
7.35 (m, 2H), 7.35 – 7.20 (m, 3H), 6.97 (dd, J = 15.0, 0.8
Hz, 1H), 6.65 (d, J = 6.0 Hz, 1H), 6.41 (dd, J = 15.0, 0.6
Hz, 1H), 2.02 (d, J = 1.3 Hz, 3 H); 13C NMR (75 MHz,
CDCl3) δ = 147.01, 139.90, 136.55, 136.37, 135.58, 133.90,
133.53, 132.45, 129.40, 128.49, 128.43, 127.64, 127.60,
109.42, 105.87, 100.84, 20.48, 13.75; IR (neat): 3060,
2922, 2154, 1598, 1445 cm-1.
methoxyphenyl)selenophene (Table 2, 2e)
In a 10 mL round bottom flask, a mixture of 1-((1E,3E)-4-
bromobuta-1,3-dien-1-yl)-2-methoxybenzene (239.1 mg, 1
mmol), KSeCN (173.0 mg, 1.2 mmol), and I2o(51.0 mg, 20
mol%) in DMSO (2.5 mL) was heated at 90 C for 10.5 h
(TLC) in an oil bath. The reaction mixture was then
allowed to cool and was extracted with EtOAc (3x20 mL).
The extract was washed with saturated Na2S2O3 (10 mL)
and water (10 mL). The organic phase was dried (Na2SO4)
and was evaporated to leave the crude product, which was
purified by column chromatography over silica gel
(EtOAc:n-hexane = 2:98) to provide the pure 2-(2-
methoxyphenyl)selenophene (2e),[12] Yield: 202 mg (85%);
1H NMR (300 MHz, CDCl3) δ = 7.94 (d, J = 5.8 Hz, 1H),
7.67 – 7.57 (m, 2H), 7.29 – 7.20 (m, 1H), 7.20 – 7.12 (m,
1H), 6.95 – 6.84 (m, 2H), 3.83 (s, 3H); 13C NMR (75 MHz,
CDCl3) δ 155.00, 143.57, 131.37, 129.10, 128.32, 127.39,
126.32, 125.17, 121.07, 111.77, 55.55.
This procedure was followed for all the reactions listed in
Scheme 5. All of these compounds were unknown and the
spectroscopic data (1H NMR, 13C NMR and IR) were
provided below.
2-Phenylselenophene (2a):[12] Reaction time (12 h); eluent,
n-hexane; yield: 170 mg (82%); 1H NMR (300 MHz,
CDCl3) δ = 7.98 (d, J = 5.5 Hz, 1H), 7.63 (d, J = 8.4 Hz,
2H), 7.53 (d, J = 3.8 Hz, 1H), 7.47 – 7.30 (m, 4H); 13C
NMR (75 MHz, CDCl3) δ = 150.95, 136.51, 130.70,
130.08, 129.01, 127.65, 126.49, 125.34.
2-(4-Methoxyphenyl)selenophene (2b):[12] Reaction time
(10 h); eluent, EtOAc/n-hexane (2%); yield: 225 mg
(95%); 1H NMR (300 MHz, CDCl3) δ 7.89 – 7.87 (m, 1H),
7.52 – 7.49 (m, 2H), 7.37-7.35 (m, 1H), 7.31-7.28 (m, 1H),
6.93-6.90 (m, 2H), 3.84 (s, 3H); 13C NMR (75 MHz,
CDCl3) δ 159.40, 150.81, 130.68, 129.47, 129.05, 127.73,
124.30, 114.41, 55.49
This procedure was followed for all the reactions listed in
Table 2, Scheme 2 and Scheme 3. For 3-substituted 1,3-
o
dienyl bromides, the reactions were carried out at 110 C.
Most of these compounds were known and their
spectroscopic data (1H NMR and 13C NMR) were provided
below. The known compounds were identified by
comparison of their spectroscopic and spectrometric data
with those reported earlier.
2-(4-Chlorophenyl)selenophene (2c):[12] Reaction time
1
(11.5 h); eluent, n-hexane; yield: 191 mg (79%); H NMR
(b) Representative experimental procedure for the
(300 MHz, CDCl3) δ = 7.97-7.95 (m, 1H), 7.51-7.43 (m,
3H), 7.35-7.30 (m, 3H); 13C NMR (75 MHz, CDCl3) δ =
149.50, 135.10, 133.46, 130.84, 130.62, 129.17, 127.67,
125.84
coupling
of
((1E,3E)-4-bromobuta-1,3-dien-1-
yl)benzene and K2S to 2-phenylthiophene (Table 4, 3a):
In a 10 mL round bottom flask, a mixture of ((1E,3E)-4-
bromobuta-1,3-dien-1-yl)benzene (209.0 mg, 1 mmol),
K2S (165.0 mg, 1.5 mmol), and I2 (51.0 mg, 20 mol%) in
2-(4-Fluorophenyl)selenophene (2d):[15a] Reaction time
1
(11.8 h); eluent, n-hexane; yield: 169 mg (75%); H NMR
o
DMF (2.5 mL) was heated at 110 C for 12 h (TLC) in an
(300 MHz, CDCl3) δ = 7.96 (d, J = 5.6 Hz, 1H), 7.56 (ddd,
J = 8.7, 5.2, 1.4 Hz, 2H), 7.42 (d, J = 3.8 Hz, 1H), 7.34
(ddd, J = 5.3, 3.8, 1.2 Hz, 1H), 7.16 – 7.04 (m, 2H); 13C
NMR (75 MHz, CDCl3) δ = 162.42 (d, J = 247.5 Hz),
149.64 , 132.80 (d, J = 3.3 Hz), 130.70 , 128.04 (d, J = 8.0
Hz), 125.38, 115.89 (d, J = 21.7 Hz).
oil bath. The reaction mixture was then allowed to cool and
was extracted with EtOAc (3x20 mL). The extract was
washed with aqueous Na2S2O3 (10 mL) and water (10 mL).
The organic phase was dried (Na2SO4) and was evaporated
to leave the crude product, which was purified by column
chromatography over silica gel (n-hexane) to provide the
[15f]
pure 2-phenylthiophene. (3a):
Yield: 125 mg (78%);
2-(4-Nitrophenyl)selenophene (2f):[15b] Reaction time (12
h); eluent, EtOAc/n-hexane (5%); yield: 202 mg (80%); 1H
NMR (300 MHz, CDCl3) δ = 8.24 – 8.14 (m, 2H), 8.10 (dd,
J = 5.6, 1.1 Hz, 1H), 7.69 – 7.59 (m, 3H), 7.37 (dd, J = 5.6,
3.9 Hz, 1H); 13C NMR (75 MHz, CDCl3) δ = 147.73,
146.66, 142.55, 133.32, 131.19, 128.10, 126.51, 124.41.
1H NMR (300 MHz, CDCl3) δ = 7.77 – 7.70 (m, 2H), 7.52
– 7.34 (m, 5H), 7.17 (dd, J = 5.1, 3.6 Hz, 1H); 13C NMR
(75 MHz, CDCl3) δ = 144.51, 134.50, 128.97, 128.08,
127.53, 126.03, 124.87, 123.17.
This procedure was followed for all the reactions listed in
Table 3 and Scheme 4. Some of these compounds were
6
This article is protected by copyright. All rights reserved.

10.1002/adsc.201701232
Advanced Synthesis & Catalysis
2-(2-Nitrophenyl)selenophene (2g):[12] Reaction time
(11.5 h); eluent, EtOAc/n-hexane (5%); yield: 186 mg
131.05, 130.15, 129.13, 128.36, 122.30, 118.70, 116.01; IR
(neat): 3457, 3364, 3055, 2925, 2851, 1613, 1490 cm-1;
anal. calcd. for C10H9NSe: C 54.07, H 4.08, N 6.31; found:
C 54.11, H 4.05, N 6.39%.
1
(74%); H NMR (300 MHz, CDCl3) δ = 8.11 (dd, J = 5.6,
1.1 Hz, 1H), 7.77 – 7.69 (m, 1H), 7.60 – 7.42 (m, 3H), 7.34
– 7.20 (m, 2H); 13C NMR (75 MHz, CDCl3) δ = 149.31,
142.87, 133.20, 132.62, 131.91, 130.69, 130.16, 129.78,
128.63, 123.91.
2-(Selenophen-2-yl)furan (2p):[15e] Reaction time (11.5
1
h); eluent, n-hexane; yield: 152 mg (77%); H NMR (300
MHz, CDCl3) δ = 7.91-7.89 (m, 1H), 7.44-7.41 (m, 2H),
7.30-7.27 (m, 1H), 6.52 (q, J = 0.6 Hz, 1H), 6.45 (q, J =
1.8 Hz, 1H); 13C NMR (75 MHz, CDCl3) δ = 151.55,
141.82, 138.50, 130.28, 129.34, 124.37, 112.01, 105.08
2-Methoxy-4-(selenophen-2-yl)phenyl acetate (2h):
Reaction time (11 h); eluent, EtOAc/n-hexane (10%);
1
yield: 263 mg (89%); brownish solid; H NMR (300 MHz,
CDCl3) δ = 7.95 (dd, J = 5.6, 1.1 Hz, 1H), 7.43 (dd, J = 3.8,
1.1 Hz, 1H), 7.32 (dd, J = 5.6, 3.8 Hz, 1H), 7.19 – 7.11 (m,
2H), 7.05 (d, J = 8.7 Hz, 1H), 3.89 (s, 3H), 2.34 (s, 3H);
13C NMR (75 MHz, CDCl3) δ = 169.00, 151.25, 150.06,
139.32, 135.53, 130.56, 130.37, 125.67, 123.17, 119.08,
110.63, 55.95, 20.67; IR (neat): 2837, 1763, 1602, 1505,
1197 cm-1; anal. calcd. for C13H12O3Se: C 52.89, H 4.10;
found: C 52.78, H 4.25%.
(E)-2-(Hept-1-en-1-yl)selenophene (2q):[12] Reaction time
1
(12 h); eluent, n-hexane; yield: 125 mg (55%); H NMR
(500 MHz, CDCl3) δ = 7.72 (d, J = 5.6 Hz, 1H), 7.16 (dd, J
= 5.7, 3.8 Hz, 1H), 7.01 (d, J = 3.7 Hz, 1H), 6.55 (d, J =
15.2 Hz, 1H), 6.00 (dt, J = 15.5, 7.0 Hz, 1H), 2.17 (qd, J =
7.1, 1.6 Hz, 2H), 1.60 – 1.23 (m, 6H), 0.98 – 0.83 (m, 3H);
13C NMR (126 MHz, CDCl3) δ = 149.68, 132.73, 129.89,
127.49, 126.81, 125.66, 32.96, 31.56, 29.03, 22.68, 14.18.
3-Chloro-2-phenylselenophene (2i):[12] Reaction time (12
1
2-(2-Methoxyphenyl)thiophene (3b):[15g] Reaction time
(10 h); eluent, EtOAc/n-hexane (2%); yield: 160 mg
h); eluent, n-hexane; yield: 179 mg (74%); H NMR (300
MHz, CDCl3) δ = 7.91 (d, J = 5.9 Hz, 1H), 7.72 – 7.66 (m,
2H), 7.51 – 7.36 (m, 3H), 7.33 (d, J = 5.9 Hz, 1H); 13C
NMR (75 MHz, CDCl3) δ = 141.33, 134.06, 132.10,
129.12, 129.09, 128.65, 128.18, 121.70.
1
(84%); H NMR (300 MHz, CDCl3) δ = 7.71 (dd, J = 7.6,
1.6 Hz, 1H), 7.57 (dd, J = 3.7, 1.1 Hz, 1H), 7.42 – 7.27 (m,
2H), 7.15 (ddd, J = 5.0, 3.7, 0.8 Hz, 1H), 7.10 – 6.99 (m,
2H), 3.96 (s, 3H); 13C NMR (75 MHz, CDCl3) δ = 155.71,
139.58, 128.68, 128.44, 126.86, 125.49, 125.42, 123.47,
121.02, 111.76, 55.62.
2,3-Diphenylselenophene (2j):[15c] Reaction time (11 h);
eluent, n-hexane; yield: 221 mg (78%); 1H NMR (300
MHz, CDCl3) δ = 7.97 (d, J = 5.7 Hz, 1H), 7.44 (d, J = 5.7
Hz, 1H), 7.30 – 7.18 (m, 10H); 13C NMR (75 MHz,
CDCl3) δ = 145.03, 140.06, 137.72, 136.48, 133.97, 129.54,
129.40, 129.15, 128.52, 128.42, 127.35, 126.88.
2-(4-Fluorophenyl)thiophene (3c):[15h] Reaction time
1
(11.8 h); eluent, n-hexane; yield: 135 mg (76%); H NMR
(300 MHz, CDCl3) δ = 7.60 (dd, J = 8.6, 5.3 Hz, 2H), 7.33
– 7.23 (m, 2H), 7.16 – 7.04 (m, 3H); 13C NMR (75 MHz,
CDCl3) δ = 164.03, 160.76, 143.40, 130.83, 130.78, 128.15,
127.73, 127.63, 124.86, 123.19, 116.04, 115.75.
3-Pentyl-2-phenylselenophene (2k):[12] Reaction time (12
1
h); eluent, n-hexane; yield: 144 mg (52%); H NMR (300
MHz, CDCl3) δ = 7.93 (d, J = 5.6 Hz, 1H), 7.52 – 7.40 (m,
4H), 7.40 – 7.30 (m, 2H), 2.66 (dd, J = 8.6, 7.2 Hz, 2H),
1.66 (dd, J = 10.2, 5.2 Hz, 2H), 1.44 – 1.23 (m, 4H), 1.07 –
0.79 (m, 3H); 13C NMR (75 MHz, CDCl3) δ = 143.36,
140.29, 136.82, 132.80, 129.61, 128.64, 128.47, 127.28,
31.76, 30.84, 29.75, 22.57, 14.13.
2-(4-Nitrophenyl)thiophene (3d):[15i] Reaction time (11.5
1
h); eluent, EtOAc/n-hexane (5%); yield: 152 mg (74%); H
NMR (300 MHz, CDCl3) δ = 8.27 – 8.20 (m, 2H), 7.77 –
7.70 (m, 2H), 7.50 – 7.42 (m, 2H), 7.15 (dd, J = 5.1, 3.7
Hz, 1H); 13C NMR (75 MHz, CDCl3) δ = 146.75, 141.71,
140.69, 128.80, 127.79, 126.13, 125.82, 124.51.
3-Hexyl-2-phenylselenophene (2l): Reaction time (12 h);
eluent, n-hexane; yield: 131 mg (45%); Yellowish gummy
liquid; 1H NMR (300 MHz, CDCl3) δ = 7.89 (d, J = 5.7 Hz,
1H), 7.45-7.27 (m, 6H), 2.61 (t, J = 7.8 Hz, 2H), 1.62-1.55
(m, 2H), 1.34-1.22 (m, 6H), 0.87 (t, J = 6.9 Hz, 3H); 13C
NMR (75 MHz, CDCl3) δ = 143.38, 140.36, 136.84,
132.85, 129.64, 128.65, 128.49, 127.31, 31.74, 31.14,
29.79, 29.25, 22.72, 14.20; IR (neat): 3023, 2985, 1546,
1444, 1243 cm-1; anal. calcd. for C16H20Se: C 65.97, H
6.92; found: C 66.01, H 6.75%.
2-(2-Nitrophenyl)thiophene (3e):[15j] Reaction time (12
1
h); eluent, EtOAc/n-hexane (5%); yield: 144 mg (70%); H
NMR (300 MHz, CDCl3) δ = 7.74 (dt, J = 8.0, 1.1 Hz, 1H),
7.61 – 7.54 (m, 2H), 7.51 – 7.39 (m, 2H), 7.13 – 7.05 (m,
2H); 13C NMR (75 MHz, CDCl3) δ = 149.52, 137.20,
132.33, 131.97, 128.68, 128.40, 127.83, 127.24, 127.21,
123.89.
3-Chloro-2-phenylthiophene (3f):[8b] Reaction time (11
1
h); eluent, n-hexane; yield: 134 mg (69%); H NMR (300
2-(Anthracen-9-yl)selenophene (2m):[15d] Reaction time
MHz, CDCl3) δ = 7.69 – 7.61 (m, 2H), 7.44 – 7.29 (m, 3H),
7.20 (d, J = 5.4 Hz, 1H), 6.96 (d, J = 5.3 Hz, 1H); 13C
NMR (75 MHz, CDCl3) δ = 136.29, 132.31, 129.39,
128.79, 128.69, 128.22, 123.94, 121.42.
1
(10.5 h); eluent, n-hexane; yield: 230 mg (75%); H NMR
(300 MHz, CDCl3) δ = 8.55 (s, 1H), 8.34 (dd, J = 5.6, 1.2
Hz, 1H), 8.06 (ddt, J = 6.5, 2.9, 1.6 Hz, 4H), 7.60 – 7.44
(m, 5H), 7.40 (dd, J = 3.6, 1.2 Hz, 1H); 13C NMR (75 MHz,
CDCl3) δ = 145.44, 132.62, 131.68, 131.36, 130.90, 129.70,
128.31, 127.79, 126.90, 125.79, 125.39.
2,3-Diphenylthiophene (3g):[15k] Reaction time (11.8 h);
eluent, n-hexane; yield: 172 mg (73%); 1H NMR (300
MHz, CDCl3) δ = 7.33 – 7.21 (m, 11H), 7.15 (d, J = 5.2 Hz,
1H); 13C NMR (75 MHz, CDCl3) δ = 138.83, 138.25,
136.73, 134.50, 130.61, 129.48, 129.27, 128.57, 128.49,
127.50, 126.97, 124.29.
2-(4-Bromophenyl)selenophene (2n): Reaction time (11
h); eluent, n-hexane; yield: 217 mg (76%); light yellowish
solid; 1H NMR (300 MHz, CDCl3) δ = 7.97 (d, J = 5.4 Hz,
1H), 7.51-7.41 (m, 5 H), 7.35-7.31 (m, 1H); 13C NMR (75
MHz, CDCl3) δ = 149.45, 135.48, 132.07, 130.81, 130.65,
127.90, 125.82, 121.49; IR (neat): 3058, 1486, 1436, 1226
cm-1; anal. calcd. for C10H7BrSe: C 41.99, H 2.47; found:
C 42.05, H 2.56%.
3-Pentyl-2-phenylthiophene (3h):[12] Reaction time (12
1
h); eluent, n-hexane; yield: 152 mg (66%); H NMR (300
MHz, CDCl3) δ = 7.45 – 7.33 (m, 4H), 7.33 – 7.26 (m, 1H),
7.19 (d, J = 5.1 Hz, 1H), 6.96 (d, J = 5.1 Hz, 1H), 2.70 –
2.59 (m, 2H), 1.60 (dddd, J = 10.8, 9.7, 7.4, 5.6 Hz, 2H),
1.34 – 1.21 (m, 4H), 0.89 – 0.80 (m, 3H); 13C NMR (75
MHz, CDCl3) δ = 138.75, 137.91, 134.97, 129.58, 129.52,
128.55, 127.35, 123.73, 31.82, 30.85, 28.74, 22.60, 14.15.
2-(Selenophen-2-yl)aniline (2o): Reaction time (10 h);
eluent, EtOAc/n-hexane (10%); yield: 175 mg (79%);
1
yellowish gummy solid; H NMR (300 MHz, CDCl3) δ =
8.06 – 8.01 (m, 1H), 7.38 – 7.31 (m, 2H), 7.31 – 7.23 (m,
1H), 7.14 (td, J = 7.7, 1.6 Hz, 1H), 6.83 – 6.73 (m, 2H);
13C NMR (75 MHz, CDCl3) δ 147.26, 143.70, 131.23,
2-(Anthracen-9-yl)thiophene (3i):[15l] Reaction time (11.5
1
h); eluent, n-hexane; yield: 185 mg (71%); H NMR (300
7
This article is protected by copyright. All rights reserved.

10.1002/adsc.201701232
Advanced Synthesis & Catalysis
MHz, CDCl3) δ = 8.54 (s, 1H), 8.11 – 8.01 (m, 2H), 7.95 –
7.87 (m, 2H), 7.64 (dd, J = 5.1, 1.2 Hz, 1H), 7.54 – 7.41
(m, 4H), 7.34 (dd, J = 5.2, 3.4 Hz, 1H), 7.23 (dd, J = 3.4,
1.2 Hz, 1H); 13C NMR (75 MHz, CDCl3) δ = 139.05,
131.99, 131.32, 129.49, 128.41, 128.05, 127.27, 126.76,
126.70, 125.98, 125.35.
14.19, 14.15; IR (neat): 2954, 2925, 2855, 2155, 1673,
1465 cm-1.
1-Methoxy-2-((1E,3E)-4-selenocyanatobuta-1,3-dien-1-
yl)benzene: Reaction time (12 h); eluent, EtOAc/n-hexane
1
(10%); yield: 56 mg (21%); yellowish gummy liquid; H
NMR (300 MHz, CDCl3) δ = 7.44 (dd, J = 7.7, 1.7 Hz, 1H),
7.33 – 7.24 (m, 1H), 7.05 – 6.93 (m, 2H), 6.92 – 6.77 (m,
2H), 6.42 (d, J = 14.4 Hz, 1H), 3.87 (s, 3H); 13C NMR (75
3-Methyl-2-phenylthiophene (3j):[15m] Reaction time
1
(11.8 h); eluent, n-hexane; yield: 100 mg (70%); H NMR
(300 MHz, CDCl3) δ = 7.54 – 7.47 (m, 2H), 7.47 – 7.39 (m, MHz, CDCl3) δ = 157.44, 143.42, 131.94, 129.98, 127.29,
2H), 7.38 – 7.31 (m, 1H), 7.23 (d, J = 5.1 Hz, 1H), 6.96 (d,
J = 5.1 Hz, 1H), 2.36 (s, 3H); 13C NMR (75 MHz, CDCl3)
δ = 137.97, 134.91, 133.27, 131.21, 129.14, 128.61, 127.26,
123.51, 15.04.
126.57, 125.03, 120.88, 111.18, 108.28, 100.70, 55.63; IR
(neat): 2934, 2837, 2153, 1615, 1463, 1247 cm-1.
Acknowledgements
2-Methoxy-4-(thiophen-2-yl)phenyl
acetate
(3k):
Reaction time (11 h); eluent, EtOAc/n-hexane (10%);
1
We are pleased to acknowledge the financial support from Indian
National Science Academy, New Delhi for the award of INSA
Senior Scientist position to B.C.R. P.M. thanks CSIR for his
fellowships.
yield: 196 mg (79%); light yellowish gummy solid; H
NMR (300 MHz, CDCl3) δ = 7.30 – 7.25 (m, 2H), 7.19 (d,
J = 7.7 Hz, 2H), 7.09 – 7.02 (m, 2H), 3.89 (s, 3H), 2.33 (s,
3H); 13C NMR (75 MHz, CDCl3) δ = 169.20, 151.36,
143.87, 139.33, 133.62, 128.11, 125.12, 123.57, 123.27,
118.69, 110.45, 56.07, 20.80; IR (neat): 3108, 2939, 1761,
1501, 1192 cm-1; anal. calcd. for C13H12O3S: C 62.89, H
4.87; found: C 62.77, H 4.31%.
References
2-(4-Chlorophenyl)thiophene (3l):[15g] Reaction time (12
[1] a) S.-H. Juang, C.-C. Lung, P.-C. Hsu, K.-S.Hsu,Y.-C.
Li, P.-C. Hong, H.-S. Shiah, C.-C. Kuo, C.-W. Huang,
Y.-C. Wang, L. Huang, T. S. Chen, S.-F. Chen, K.-C.
Fu, C.-L. Hsu, M.-J. Lin, C.-J. Chang, C. L. Ashendel,
T. C. K. Chan, K.-M. Chou, J.-Y. Chang, Mol. Cancer
Ther. 2007, 6, 193; b) H.-S. Shiah, W.-S. Lee, S.-H.
Juang, P.-C. Hong,C.-C. Lung,C.-J. Chang, K.-M.Chou,
J.-Y. Chang, Biochem. Pharmacol. 2007, 73, 610.
1
h); eluent, n-hexane; yield: 161 mg (83%); H NMR (300
MHz, CDCl3) δ = 7.59 – 7.50 (m, 2H), 7.40 – 7.33 (m, 2H),
7.30 (dq, J = 3.8, 1.2 Hz, 2H), 7.10 (dd, J = 5.0, 3.8 Hz,
1H); 13C NMR (75 MHz, CDCl3) δ = 143.16, 133.27,
133.01, 129.11, 128.24, 127.18, 125.28, 123.54.
((1Z,3E)-4-Selenocyanatobuta-1,3-diene-1,2-
diyl)dibenzene and ((1E,3E)-4-selenocyanatobuta-1,3-
diene-1,2-diyl)dibenzene: Reaction time (12 h); eluent,
EtOAc/n-hexane (10%); yield: 214 mg (69%); yellowish
[2] E. A. Wilhelm, C. R. Jesse, C. F. Bortolatto, C. W.
1
gummy liquid; H NMR (300 MHz, CDCl3) δ = 7.49 –
Nogueira, L. Savegnago, Brain Res. Bull. 2009, 79, 281.
7.34 (m, 8H), 7.23 – 7.07 (m, 7H), 6.96 – 6.89 (m, 2H),
6.74 (s, 1H), 6.70 (s, 1H), 6.37 (d, J = 15.3 Hz, 1H), 5.90
(d, J = 14.7 Hz, 1H); 13C NMR (75 MHz, CDCl3) δ =
145.83, 140.29, 139.35, 138.83, 138.80, 136.60, 135.65,
134.92, 133.93, 129.81, 129.66, 129.41, 129.36, 129.01,
128.71, 128.65, 128.25, 128.19, 128.12, 128.01, 113.40,
109.29, 100.57; IR (neat): 3057, 2924, 2854, 2155, 1673,
1446 cm-1.
[3] E. A. Wilhelm, C. R. Jesse, S. S. Roman, C. W.
Nogueira, L. Savegnago, Exp. Mol. Pathol. 2009, 87,
20.
[4] S. W. May, L. Wang, M. M. Gill-Woznichak, R. F.
Browner, A. A. Ogonowski, J. B. Smith, S. H. Pollock,
J. Pharm. Exp. Ther. 1997, 283, 470.
((E)-2-((E)-2-Selenocyanatovinyl)hept-1-en-1-
yl)benzene and ((Z)-2-((E)-2-selenocyanatovinyl)hept-1-
en-1-yl)benzene: Reaction time (12 h); eluent, EtOAc/n-
hexane (10%); yield: 240 mg (79%); yellowish gummy
[5] a) S. W. May, Expert Opin. Invest. Drugs 2002, 11,
1261; b) E. A. Wilhelm, C. R. Jesse, C. F. Bortolatto, C.
W. Nogueira, L. Savegnago, Pharmacol. Biochem.
Behav. 2009, 93, 419; c) T. Gobel, L. Gsell,O. F. Huter,
P. Maienfisch, R. Naef, A. C. O. Sullivan, T. Pitterna,
T. Rapold, G. Seifert, M. Sern, H. Szczepanski, D. J.
Wadsworth, Pestic. Sci. 1999, 55, 355.
1
liquid; H NMR (300 MHz, CDCl3) δ = 7.44 – 7.34 (m,
4H), 7.29 (dt, J = 9.3, 3.4 Hz, 4H), 7.26 – 7.13 (m, 3H),
6.87 (dd, J = 15.1, 0.8 Hz, 1H), 6.64 (s, 1H), 6.58 (s, 1H),
6.53 (d, J = 15.3 Hz, 1H), 6.42 (d, J = 15.1 Hz, 1H), 2.64 –
2.12 (m, 4H), 1.72 – 1.45 (m, 4H), 1.37 (td, J = 7.1, 3.2 Hz,
8H), 1.07 – 0.79 (m, 6H); 13C NMR (75 MHz, CDCl3) δ =
146.39, 139.52, 139.05, 136.91, 136.55, 136.52, 135.27,
132.78, 129.47, 128.96, 128.54, 128.47, 127.68, 127.56,
108.86, 105.60, 100.87, 100.69, 33.87, 32.15, 31.80, 28.62,
28.34, 27.41, 22.62, 22.48, 14.18, 14.14; IR (neat): 2956,
2928, 2858, 2155, 1672, 1598, 1466 cm-1.
[6] a) L. K. T., Lam, N. Ahamed, U.S. Pat. Appl. Publ.
20020165215, 2002; b) R. Mishra, K. K. Jha, S. Kumar,
I. Tomer, Der. Pharma. Chemica 2011, 3, 38; c) M.
Ronsheim, G.-L.Araldi, Indazole derivatives useful as
melanin concentrating receptor ligands. PCT patent
application WO 2008061109 (A2) (2008).
((E)-2-((E)-2-Selenocyanatovinyl)oct-1-en-1-yl)benzene
and
((Z)-2-((E)-2-selenocyanatovinyl)oct-1-en-1-
yl)benzene: Reaction time (12 h); eluent, EtOAc/n-
hexane (10%); yield: 245 mg (77%); yellowish gummy
liquid; H NMR (300 MHz, CDCl3) δ = 7.38 (dd, J = 8.1,
[7] C. Paal, Ber. Dtsch. Chem. Ges. 1885, 18, 2255.
1
[8] a) R. F. Schumacher, A. R. Rosario, A. C. G. Souza, P.
H. Menezes, G. Zeni, Org. Lett. 2010, 12, 1952; b) R. F.
Schumacher, A. R. Rosario, M. R. Leite, G. Zeni,
Chem. Eur. J. 2013, 19, 13059.
6.6 Hz, 3H), 7.29 (dt, J = 9.7, 3.6 Hz, 4H), 7.25 – 7.15 (m,
2H), 6.86 (dd, J = 15.1, 0.8 Hz, 1H), 6.64 (s, 1H), 6.58 (s,
1H), 6.53 (d, J = 15.3 Hz, 1H), 6.42 (d, J = 15.0 Hz, 1H),
2.59 – 2.20 (m, 4H), 1.55 (tt, J = 7.7, 5.6 Hz, 4H), 1.34 (dq,
J = 9.9, 2.4 Hz, 11H), 1.07 – 0.74 (m, 5H); 13C NMR (75
MHz, CDCl3) δ = 146.37, 139.49, 139.04, 136.91, 136.54,
136.52, 135.25, 132.76, 129.46, 128.96, 128.53, 128.46,
127.67, 127.55, 108.86, 105.60, 100.86, 100.68, 33.90,
31.76, 31.58, 29.62, 29.28, 28.87, 28.61, 27.43, 22.72,
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FULL PAPER
Iodine Catalyzed Synthesis of Chalcogenophenes
by the Reaction of 1,3-Dienyl Bromides and
KSeCN/K2S
Adv. Synth. Catal. Year, Volume, Page – Page
Pintu Maity and Brindaban C. Ranu*
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