(Biphenyl-2-alkyne) derivatives as common precursors for the synthesis of 9-iodo-10-organochalcogen-phenanthrenes and 9-organochalcogen-phenanthrenes

Article abstract of DOI:10.1039/c6ob01807f

In this paper, we report our results on the cyclization of (biphenyl-2-alkyne) derivatives to give two different types of phenanthrene derivatives, 9-iodo-10-organochalcogen-phenanthrenes and 9-organochalcogen-phenanthrenes. The strategy for the synthesis was based on the use of electrophilic cyclization for the preparation of 9-iodo-10-organochalcogen-phenanthrenes and iron(iii) chloride/diorganyl diselenide-mediated intramolecular cyclization to prepare 9-organochalcogen-phenanthrenes. The effects of solvent, temperature, reaction time and stoichiometry on the efficiency of cyclization reactions were investigated. The standard reaction conditions were compatible with many functional groups in the substrates, such as methyl, chlorine, fluorine and methoxyl. This protocol was efficient for diorganyl diselenides and disulfides but ineffective for diorganyl ditellurides. The resulting phenanthrenes were further functionalized through Sonogashira reactions followed by the electrophilic cyclization reaction to give the selenophene-fused aromatic compounds.

Full text of DOI:10.1039/c6ob01807f

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(Biphenyl-2-alkyne) Derivatives as Common Precursors to the Synthesis
of 9-Iodo-10-organochalcogen-phenanthrenes and 9-organochalcogen-
phenanthrenes
Tamiris B. Grimaldi,a Guilherme Lutz,a Davi F. Backb and Gilson Zenia,*
5
Received (in XXX, XXX) Xth XXXXXXXXX 201X, Accepted Xth XXXXXXXXX 201X
First published on the web Xth XXXXXXXXX 200X
DOI: 10.1039/b000000x
Abstract:
In this paper, we report our results on the cyclization of (biphenyl-2-alkyne) derivatives to give two different types of
10 phenanthrene derivatives; 9-iodo-10-organochalcogen-phenanthrenes and 9-organochalcogen-phenanthrenes. The strategy for
the synthesis was based on the use of electrophilic cyclization to the preparation of 9-iodo-10-organochalcogen-phenanthrenes
and iron(III) chloride/diorganyl diselenides-mediated intramolecular cyclization to prepare 9-organochalcogen-phenanthrenes.
The effects of solvent, temperature, reaction time and stoichiometry on efficiency of cyclization reactions were investigated.
The standard reaction conditions were compatible with many functional groups in the substrates, such as methyl, chlorine,
15 fluorine and methoxyl. This protocol was efficient to diorganyl diselenides and disulfides but ineffective with diorganyl
ditellurides. The resulting phenanthrenes were further functionalized through Sonogashira reactions followed by the
electrophilic cyclization reaction to give the selenophene-fused aromatic compounds.
number of known methods to functionalize phenanthrenes at the
9-position, the chemistry to introduce reactive groups in both 9-
Introduction
and 10-positions is still scarce in the literature.22 The methods
20 The importance of polycyclic aromatic hydrocarbons derives
from their well-known physical and chemical properties as well
as biological activities. For example, mitoxantrone, daunorubicin
and doxorubicin, belonging to class of antitumoral agents used in
clinical with broad application in the treatment of several
25 leukemia as well as in combination chemotherapy of solid
55 available for the functionalization of the 9-position involve the
electrophilic cyclization of arene-containing acetylenes,23
palladium-catalyzed annulation of biphenyl aryl acetylenes,24 and
oxidative radical cyclization of biphenyl aryl acetylenes.25
Larock reported the preparation of 9-iodo-10-phenylphenanthrene
60 via electrophilic cyclization of 2-(1-alkynyl)biphenyls.23c This
methodology accommodates aryl and heteroaryl groups in the 10-
position and halogens in the 9-postion of the phenanthrene.
However, none of the desired selenium-containing products in the
9-position was obtained when using PhSeCl. In this case, only
65 the product of reduction of carbon-carbon triple bond by
phenylselenyl chloride addition was obtained. In order to
introduce two different functional groups at the 9 and 10-
positions of phenanthrene rings, in a one-step reaction, which
could undergo reactions selectively, we explored if (biphenyl-2-
70 alkyne) derivatives 1 can be used as a common starting material
to prepare both 9-iodo-10-organochalcogen-phenanthrenes 2 and
9-organochalcogen-phenanthrenes 3 (Scheme 1).
tumors.1
Anthracyclines, acridines, and ellipticines were
identified as DNA-intercalating that are thought to poison
topoisomerases I and II.2 Recently, Enbinobin, a phenanthrene
quinone, isolated from Dendrobium nobile Lindl3 not only known
30 as a potent antitumor4 and an anti-inflammatory agent,5 but also
as anti-HIV,6 antiplatelet aggregation,7 and antioxidant,8 have
been synthesized in an overall yield of 10%.9 Furthermore,
polycyclic aromatic hydrocarbons have emerged in recent years
as promising candidates in the development of electronic and
35 optical materials.10 Some phenanthrene derivatives have been
widely used as the building blocks of substances with
optoelectronic properties that include: organic semiconductors,11
fluorescence sensors, nonlinear optical materials, organic light-
emitting diode,12 electroluminescence and photoluminescence
40 applications13 and organic solar cells.14 From a synthetic point of
view, the phenanthrene structures have been extensively modified
at its 3,6- or 9,10-positions through covalent bonding, while the
reactivity of the 2,7-positions is less reactive.15 Because of the
above application the development of methods for functionalized
45 phenanthrene derivatives have attracted an impressive array of
synthetic efforts. Generally, the key synthetic aspect of the most
common advances toward phenanthrenes has been the use of
Scheme 1: General scheme.
75 Results and Discussion
In our research group, two general strategies to the synthesis of
carbon- and heterocycles containing selenium have been used: 1)
the addition of either electrophilic or nucleophilic selenium
reagents to appropriate active acyclic precursors, which promotes
80 the intramolecular cyclization. 2) to apply a suitable cyclization
photocyclization,16
metalation
followed
by
catalyzed
cyclization,17 cycloisomerization,18 Lewis acid mediated
50 cyclization reaction,19 transition metal rearrangement of alkene-
alkynes20 and olefin metathesis.21 In contrast to the impressive
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methodology to previous proper prepared organoselenium
substrates. Here we evaluated that the second one is the best way
to get the phenanthrene derivatives 2 and 3. Thus, to the
preparation of starting material (biphenyl-2-alkyne) derivatives 1,
we first prepared the geminal dibromide A as described in
Scheme 2. The reaction of A with nBuLi (1 equiv) in THF at -78
oC for 30 min followed by the addition of elemental selenium (1
equiv) and alkyl halide gave (biphenyl-2-alkyne) derivatives 1.
In order to carry out the introduction of an organochalcogen at
Scheme 2: Preparation of (biphenyl-2-alkyne) derivatives 1
5
10 the 9-position and an iodide at the 10-position of phenanthrene,
the condition described by Larock23d was applied to (biphenyl-2-
ethynyl) selenide 1b. Thus, the addition of I2 (3.0 equiv) and
NaHCO3 (3.0 equiv) at room temperature to a solution of
(biphenyl-2-ethynyl) selenide 1b in CH2Cl2 (3 mL) proved
15 disappointing with 13% isolated yields produced, even on
extending reaction times and increasing the temperature. For
further optimization of the reaction conditions, the increase in the
yields of the cyclized product 2b was observed by using THF as
solvent (Table 1, entry 1). With the aim of evaluating the effect
20 of temperature, we ran the reaction at 60 oC, which did not
improve the reaction efficacy (Table 1, entry 2). Additional
screening revealed that the yield of 9-iodo-10-butylseleno-
phenanthrene 2b was not significantly modified by using an open
tube instead of inert atmosphere (argon), thus we chose it for
25 further experiments (Table 1, entry 3). Next, our experimental
protocol turned to the effect of iodine amount. The decrease in
the amount of iodine to 2 equiv gave the product in moderated
yield, while the reduction to 1 equiv led to obtain 2b in a poor
yield (Table 1, entries 4-5). Among the solvents tested, THF and
30 acetonitrile were the most suitable for this reaction (Table 1,
entries 9-14). As can be seen from Table 1, K2CO3 was found the
most effective base for the cyclization reaction as better yield and
shorter reaction time were obtained (Table 1, entries 15-20). To
test the effect of concentration on the yield of reaction, 1.0 mL of
35 THF was used instead of 3 mL and a reduction in the yield of 9-
iodo-10-butylseleno-phenanthrene 2b was obtained (Table 1,
entry 21). We observed that 3h was the required time taken for
the reactions to be completed in good yields (Table 1, entries 22-
25). On the basis of optimization study, we conclude that the
40 reaction of (biphenyl-2-ethynyl) selenide 1b (0.25 mmol) in THF
(3 mL) with iodine (3 equiv) and K2CO3 (0.5 equiv), under room
temperature for 3 h is the best condition to obtain the 9-iodo-10-
butylseleno-phenanthrene 2b in higher yield (Table 1, entry 23).
55
Figure 1. ORTEP view of the compound 2b (CCDC 1495950)
Table 1: Effect of different reaction parameters on the
preparation of 9-iodo-10- butylseleno-phenanthrene 2ba
entry
I2 (equiv)
base (equiv)
NaHCO3 (2)
NaHCO3 (2)
NaHCO3 (2)
NaHCO3 (2)
NaHCO3 (2)
NaHCO3 (1)
NaHCO3 (0.5)
-
NaHCO3 (0.5)
NaHCO3 (0.5)
NaHCO3 (0.5)
NaHCO3 (0.5)
NaHCO3 (0.5)
NaHCO3 (0.5)
Na2CO3 (0.5)
NaOH (0.5)
K2CO3 (0.5)
Cs2CO3 (0.5)
CH3COONa (0.5)
t-BuOK (0.5)
K2CO3 (0.5)
K2CO3 (0.5)
K2CO3 (0.5)
K2CO3 (0.5)
solvent
THF
THF
THF
THF
THF
THF
THF
THF
CH2Cl2
EtOH
CH3NO2
CH2CN
DMF
hexane
THF
THF
THF
THF
THF
yields (%)b
85 (65)c
79 (68)c, d
78 (73)
58
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
3
3
3
2
1
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
32
81 (75)
78 (74)
57
13
26
23
62
05
14
83 (75)
78
87 (71)
87 (66)
73
The
structural
assignment
of
9-iodo-10-butylseleno-
45 phenanthrenes was based on NMR analysis and confirmed by X-
ray diffraction, which showed the exact position of the
cyclization as a 6-endoꢀdig process (Figure 1, CCDC 1495950).
THF
THF
THF
THF
69
7e
89f
84 (71)g
79h
THF
60 [a] The reaction was performed by the addition of iodine and base to a
solution of (biphenyl-2-ethynyl) selenide 1b (0.25 mmol) in solvent (3
mL), at room temperature, under air atmosphere. [b] Yields are determined
by gas chromatography using dodecane as internal standard. In parentheses
isolated yields after column chromatography. [c] Reaction was carried out
65 under argon atmosphere. [d] Reaction was carried out at 60oC. [e] THF (1
mL) was used. [f] Reaction ran at room temperature for 5h. [g] Reaction
ran at room temperature for 3h. [h] Reaction ran at room temperature for
2h. [i] Reaction ran at room temperature for 1h.
50 i) p-toluenesulfonic acid (0.02 mol%), toluene, reflux, 18h; ii)
Pd(PPh3)2Cl2 (10 mol%), THF, 60 ºC, 18h; iii) FeCl3.6H2O (1.1 equiv.),
reflux, CH2Cl2, 0.5h; iv) CBr4 (1.25 equiv.), PPh3 (2.0 equiv.), CH2Cl2, 0
ºC to r.t., 1h; v) 1) BuLi (2.1 equiv.), THF, -78 ºC; to r.t.
2
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In order to examine the efficiency of this protocol, the above
optimized reaction conditions were applied to other 65 bond exhibits an easier heterolytic cleavage than that of the
tellurium IV intermediate II (Scheme 3).26 The Csp-tellurium
functionalized (biphenyl-2-ethynyl) selenides and the results
obtained are shown in Table 2. Most of the reactions proceeded
carbon-sulfur and carbon-selenium bonds, due to the large
volume and greater ionic character of the tellurium atom and the
easy polarization of the bonds27 Thus nucleophilic attack of
iodide anion on the carbon-tellurium bond on telluride III
5
smoothly
to
afford
the
corresponding
9-iodo-10-
organochalcogen-phenanthrenes 2 in good to excellent yields.
Unsubstituted aromatic ring in the (biphenyl-2-ethynyl) selenide 70 produces the unstable tellurium tetraiodide and alkynyl iodide 4
could be cyclized to phenanthrene 2a in 46% yield, however; this
substrate required the use of reflux temperature (Table 2, 2a). The
10 aromatic ring of biphenyl system with a methyl group at the
(Scheme 3). Concerning the substrates bearing electron-
withdrawing groups at the para-position of the distal phenyl ring,
we found additional limitations in this methodology. For
example no reaction was observed with ester, nitro and chlorine
ortho-, meta- and para-position reacted smoothly; however,
ortho-methyl group bounded to the aromatic ring reduced the 75 groups and unfortunately, all conditions tested were found to be
reactivity (Table 2, 2b-2d). Probably, the steric hindrance
exerted by the methyl group on the ortho position decreased the
15 reactivity for the nucleophilic attack at the carbon-carbon triple
bond. When we carried out the cyclization of (biphenyl-2-
ethynyl) selenide with meta-methyl group, under optimized
reaction conditions, a 1:0.4 regioisomeric mixture was obtained
in high overall yields with cyclization to the less hindered
20 position being favored (Table 2, 2c and 2c'). In the case of
substrate, which has a methoxyl group at the para-position, the
iodonium ion-induced intramolecular ipso-cyclization giving the
mixture of phenanthrene 2e and cyclohexadienone 2e' in 33% and
53% yields, respectively (Table 2, 2e and 2e'). On the other
25 hand, running the reaction of (biphenyl-2-ethynyl) selenide,
bearing a methoxyl group at meta position, under optimized
reaction conditions, a 4:1 regioisomeric mixture was obtained in
high overall yields (Table 2, 2f and 2f'). We also found that the
reaction with the steric hindrance naphthyl group worked well
30 under the standard reaction conditions, leading to the formation
of the expected product in good yield (Table 2, 2g). Next, we
tested the influence of electronic effects of different substituents
at the aromatic ring directly bonded to alkyne (Table 2). The
experimental results showed that these substrates also worked
35 well under the standard reaction conditions; although, the
presence of an electron-withdrawing group on the aromatic ring
decreased the yield (Table 2, 2h-2j). We also evaluated the
reactivity of (biphenyl-2-ethynyl) selenides having aryl groups at
the selenium atom (Table 2). While aryl selenides bearing a
40 neutral, electron-donating and steric hindrance naphthyl groups
on the aromatic ring provided the best yields of products, the
presence of an electron-withdrawing group decreased the yields
(Table 2, 2k-2p). We extended the optimized conditions to
(biphenyl-2-ethynyl) sulfides and the results showed that this
45 cyclization reaction was not sensitive to the electronic effects of
substituents directly bonded to the sulfur atom. Methyl and
phenyl were compatible with the reaction conditions yielding the
corresponding phenanthrenes 2q-s in moderated to good yields
(Table 2, 2q-s). The use of an iodo-alkyne derivative, instead of
50 selenides or sulfides was also tested and the reaction system was
suitable for the cyclization, giving the desired cyclized product in
95% yield (Table 2, 2t). This result is significant because there
are many ways to transform the resulting iodide functionalities
into other substituents. Furthermore, we did not observe any
55 reaction when (biphenyl-2-ethynyl) with different functions, such
as trimethylsilyl, diethyl phosphonate, propargyl alcohol, and
aldehyde was subjected to this cyclization protocol under the
optimized reaction conditions (Table 2). When a phenyl
tellurium group was introduced at the carbon-carbon triple bond
60 of (biphenyl-2-ethynyl), the iodo-alkyne 4 product was formed
and any amount of cyclized product was obtained (Scheme 3).
We believe that because of great affinity between tellurium and
iodine atoms the formation of iodo-alkyne 4 goes through a
ineffective to produce the cyclized product.
Table 2: Synthesis of 9-iodo-10-organochalcogen-phenanthrenes
2a, b
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YR1
The previous investigation of Larock and co-workers utilized
PhSeCl as electrophilic source in the cyclization reaction of 2-(1-
10 phenylethynyl) biphenyl, aiming the introduction of PhSe at the
9-position of phenanthrenes. However, the product of PhSeCl
addition to alkyne was obtained instead of cyclized product.23c
Our group and other have made new approaches regarding the
use of iron salts and diorganyl diselenides, as cyclizing agents, in
I
YR1
R2
K2CO3 (0.5 equiv.)
THF, air, r.t.
I2
+
(3 equiv)
R2
I
I
I
I
SenBu
SenBu
SenBu
SenBu
+
15 the preparation of carbon- and heterocycles28
The main
advantage of this methodology is that diorganyl diselenide
reagents have dual role by acting as cyclizing agent and to
incorporate both portions of diorganyl diselenides (2 RSe) in the
final product, thus providing a more useful and valuable method
20 in terms of atom economy. In particular, the incorporation of an
organoselenium group in the carbocycle is of considerable
interest given its applications in different reactions in the organic
synthesis29 as well as its biological properties.30 In addition, iron
reagents have appeared as an attractive alternative to other
25 transition metals due to their relative stability, abundance, low
toxicity, economic and ecologic advantages, and excellent
tolerance towards various functional groups.31 Because of our
aim is to develop a method to introduce an organoselenium
moiety in the 9-position of phenanthrene we first chose an
30 optimized reaction condition and applied to 2-(1-phenylethynyl)
biphenyl (Table 3). Optimized reaction conditions utilized
consisted the addition of diorganyl diselenide (1.0 equiv) to a
FeCl3 (2.0 equiv) solution in dichloromethane (2.0 mL), under
argon atmosphere, at room temperature. After 15 min, at this
35 temperature, 2-(1-phenylethynyl) biphenyl 4 (0.25 mmol) was
added. The resulting mixture was stirred at room temperature for
the time indicated in Table 3. We observed that functional
groups bounded to the aromatic ring of diaryl diselenides
influenced the yields of 9-organochalcogen-phenanthrenes 3.
40 However, because the yields varied with both electron-donating
and electron-withdrawing groups, could not establish any clear
relationship between the effect of substituents and the reaction
yield (Table 3, 3a-i). When the reaction was carried out using
diorganoyl disulfides, 9-organothio-phenanthrenes 3j and 3k
45 were obtained in poor yields, presumably the strength of the
sulfur-sulfur bond, when compared with that of selenium-
selenium bond, hamper its heterolytic cleavage. Furthermore,
(biphenyl-2-ethynyl) having different functions at the alkyne
terminus, such as, selenides, iodine, trimethylsilyl, diethyl
50 phosphonate, propargyl alcohol and aldehyde failed to afford the
desired products under the standard reaction conditions and only
decomposition of starting material was observed (Table 3).
Additional limitation in our method was observed when
(biphenyl-2-alkyne) derivatives bearing an electron-withdrawing
55 group at the para-position of the distal phenyl ring, was reacted
under optimized reaction conditions. In these cases gave no
cyclized product was obtained and the starting material was
recovered.
2b 71% (3h)
2a 46% (12h)
2c:2c' 79% 1:0.4 (3h)
I
I
I
SenBu
SenBu
SenBu
+
O
OMe
2d 82% (12h)b
2e' 53% (3h)
2e 33% (3h)
I
I
I
SenBu
SenBu
SenBu
+
OMe
2g 70% (3h)
2f:2f' 90% 1:0.3 (3h)
OMe
I
I
I
I
SePh
F
SenBu
SenBu MeO
SenBu
2h 60% (3h)
2i
82% (3h)
I
2k 75% (3h)
2j 45% (12h)
I
I
Se
Se
OMe
Se
2m 77% (3h)
2n 60% (3h)
2l 81% (3h)
I
I
I
Se
Cl
SMe
Se
F
2o 46% (3h)
2q 55% (3h)
2p 40% (12h)
I
I
I
SEt
SPh
I
2t 95% (12h)b
2r 65% (3h)
2s 77% (3h)
I
I
I
SenBu
SenBu
SiMe3
F
Cl
not formed
not formed
not formed
I
O
I
I
I
O
P(OEt)2
TePh
OH
not formed
not formed
not formed
not formed
[a] The reactions were performed by the addition of iodine (3.0 equiv)
and K2CO3 (0.5 equiv)to a solution of (biphenyl-2-ethynyl) selenides 1
(0.25 mmol) in THF (3 mL), at room temperature, under air atmosphere.
[b] Yields of purified products
Based on these experimental results and the knowledge that iron
60 salts react with diorganyl diselenides promoting the Se-Se bond
heterogeneous cleavage to give an organoselenyl cation and an
organoselenyl anion,32 we propose that this cyclization most
likely proceeds via the pathway outlined in Scheme 4. The
iron(III) coordination with one selenium atom from diorganyl
65 diselenide activating the other towards nucleophilic attack by the
alkyne giving the seleniranium ion IV. The attack of the electron
cloud from the aromatic ring at the activated intermediate IV
produces the cyclized species V. The reductive elimination from
V gives the stabilized carbocation VI. The removal of the
5
Scheme 3: Formation of the iodoalkyne 4
4
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hydrogen by breaking the C-H, promoted by selenolate anion,
restores the aromatic system giving the cyclized product (Scheme
4).
5
Table 3. Synthesis of 9-organochalcogen-phenanthrenes 3a, b
Scheme 4: Proposed mechanism.
Considering the high reactivity of phenanthrene at 9- and 10-
20 positions, our methodology offers two possibilities to prepare
more functionalized phenantrenes. One of them is the transition
metal-catalyzed processes, such as Sonogashira, Suzuki, Stille,
Heck, Neghishi and Ullmann cross-coupling in the Csp2-I bond at
the 10-position. The second one is the formation of a new
25 carbon-carbon bond through nickel33 or palladium-catalyzed34
cross-coupling in the Csp2-Se bond at the 9-position. Thus, the
utility of phenanthrene derivatives was initially studied through
Sonogashira reaction35 followed by the electrophilic cyclization36
reaction to give the selenophene-fused aromatic compounds
30 (Scheme 5). For this purpose, the 9-iodo-10- butylseleno-
phenanthrene 2b reacted with terminal alkynes under
a
Sonogashira condition giving 9-alkynyl-phenanthrenes 5a and 5b
in 90% and 94% yields, respectively. In the presence of
electrophilic iodine species, phenanthrenes 5a and 5b gave fused
35 selenophenes 6a and 6b in 71% and 67% yields, respectively
(Scheme 5).
[a] The reactions were carried out by addition of FeCl3 (2.0
equiv.) to a solution of aryl disselenide (1.1 equiv) in dry CH2Cl2
10 (2 mL). The resulting solution was stirred at room temperature
under argon atmosphere for 15 minutes. After that a solution of
aryl (biphenyl-2-ethynyl) 1 (0.25 mmol) in CH2Cl2 (1 mL) was
added. The resulting solution was stirred at room temperature
until complete consumption of the starting material. [b] Yields of
15 purified products.
i) Pd(PPh3)2Cl2 (5 mol%), CuI (2 mol%), Et3N, r.t., 18h; ii) I2 (3 equiv.),
CH2Cl2, r.t., 1h
40 Scheme 5: Application of 9-iodo-10-butylseleno-phenanthrene in
the preparation of fused selenophenes 5a and 5b.
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(79%). The combined chemical shifts are reported. 1H NMR
60 (CDCl3, 400 MHz): δ 8.75 (d, J = 8.5 Hz, 1H), 8.54-8.51 (m, 1H),
8.46-8.43 (m, 2H), 8.37 (s, 1H), 8.45-8.32 (m, 0.4H), 7.60-7.44
(m, 4H), 7.39-7.35 (m, 1.5H), 2.96 (t, J = 7.4 Hz, 2H), 2.90 (s,
1H), 2.71 (t, J = 7.4 Hz, 1H), 2.56 (s, 3H), 1.61 (quint, J = 7.4
Hz, 2H), 1.38 (sex, J = 7.4 Hz, 2H), 1.32-1.23 (m, 1H), 1.15 (sex,
65 J = 7.4 Hz, 1H), 0.82 (t, J = 7.4 Hz, 3H), 0.64 (t, J = 7.4 Hz, 1H).
13C RMN (CDCl3, 100 MHz): δ 139.2, 137.2, 136.8, 136.7,
136.6, 135.7, 134.2, 133.7, 133.4, 133.2, 132.1, 131.6, 131.1,
131.0, 130.8, 130.6, 129.6, 128.0, 127.9, 127.7, 127.5, 126.5,
122.9, 122.8, 122.7, 120.9, 120.8, 118.8, 33.5, 32.2, 31.8, 31.4,
70 26.1, 23.1, 22.7, 21.9, 13.6, 13.4. MS (EI, 70 eV) m/z (relative
intensity): 455 (3), 454 (26), 271 (79), 270 (28), 269 (92), 268
(28), 267 (58), 192 (32), 191 (85), 190 (37), 189 (100), 163 (27).
HRMS Calcd for C19H20ISe (M + H+): 454.9775. Found:
454.9781.
Conclusion
In summary, we demonstrated that (biphenyl-2-alkyne)
derivatives can be used as common starting materials to the
preparation of both 9-iodo-10-organochalcogen-phenanthrenes
5
and
9-organochalcogen-phenanthrenes
via
electrophlic
cyclization and iron(III) chloride and diorganyl diselenides-
mediated intramolecular cyclization, respectively. This
methodology was carried out at room temperature, using
inexpensive and environmentally friendly iron salts as metallic
10 source and under air atmosphere. The obtained products proved
to be suitable substrates for the preparation of selenophene-fused
aromatic compounds via Sonogashira reactions followed by the
electrophilic cyclization reaction.
Experimental Section
15 General Procedure for the Synthesis of 9-iodo-10-
organochalcogen-phenanthrenes 2: To a Schlenck tube, under
ambient atmosphere, at room temperature, containing (biphenyl-
2-alkyne) derivatives 1 (0.25 mmol) in THF (3 mL) were added
K2CO3 (0.5 equiv) and I2 (3.0 equiv) and the reaction mixture
20 was stirred until complete consumption of the starting material.
The reaction was quenched by the addition of a saturated aqueous
solution of Na2S2O3 (5 mL). The mixture was extracted with
ethyl acetate (3 x 5 mL) and the combined organic extracts were
dried over MgSO4, filtered and concentrated in vacuo. The
25 residue was purified by column chromatography over silica gel
using hexane and ethyl acetate as eluent to provide phenanthrenes
2.
75 Butyl(10-iodo-5-methylphenanthren-9-yl)selane (2d): Isolated
by column chromatography (hexane and ethyl acetate 99:1 as
1
eluent) as a yellow oil. Yield: 0.092 g (82%). H NMR (CDCl3,
400 MHz): δ 8.84 (ddd, J = 8.2 Hz, J = 1.5 Hz, J = 0.5 Hz, 1H),
8.54-8.48 (m, 2H), 7.55-7.52 (m, 2H), 7.48-7.46 (m, 1H), 7.43-
80 7.40 (m, 1H), 3.00 (s, 3H), 2.96 (t, J = 7.4 Hz, 2H), 1.61 (quint, J
= 7.4 Hz, 2H), 1.37 (sex, J = 7.4 Hz, 2H), 0.81 (t, J = 7.4 Hz,
3H). 13C RMN (CDCl3, 100 MHz): δ 133.9, 136.4, 135.1, 134.9,
134.3, 132.0, 131.9, 131.5, 130.9, 127.6, 127.3, 126.8, 126.2,
119.7, 32.0, 31.5, 26.9, 23.0, 13.5. MS (EI, 70 eV) m/z (relative
85 intensity): 454 (47), 453 (4), 271 (100), 270 (45), 269 (78), 268
(37), 267 (44), 191 (72), 190 (29), 189 (91), 179 (31). HRMS
Calcd for C19H20ISe (M + H+): 454.9775. Found: 454.9778.
Butyl(10-iodophenanthren-9-yl)selane (2a): Isolated by column
Butyl(10-iodo-7-methoxyphenanthren-9-yl)selane
Isolated by column chromatography (hexane and ethyl acetate
90 97:3 as eluent) as a yellow oil. Yield: 0.039 g (33%). H NMR
(2e):
chromatography (hexane and ethyl acetate 99:1 as eluent) as a
1
1
30 yellow oil. Yield: 0.05 g (46%). H NMR (CDCl3, 400 MHz): δ
8.88 (d, J = 8.2 Hz, 1H), 8.59 (d, J = 8.2 Hz, 1H), 8.51 (d, J = 8.2
Hz, 1H), 8.47 (d, J = 8.2 Hz, 1H), 7.64-7.53 (m, 4H), 2.97 (t, J =
7.4 Hz, 2H), 1.63 (quint, J = 7.4 Hz, 2H), 1.39 (sex, J = 7.4 Hz,
2H), 0.82 (t, J = 7.4 Hz, 3H). 13C RMN (CDCl3, 100 MHz): δ
35 139.3, 136.8, 133.9, 133.6, 133.2, 131.2, 130.5, 128.1, 127.8,
127.8, 127.3, 122.9, 122.6, 120.1, 32.1, 31.4, 23.0, 13.5. MS (EI,
70 eV; m/z (relative intensity)): 440 (34), 439 (2), 257 (100), 256
(49), 255 (53), 254 (42), 253 (28), 177 (22), 176 (67), 165 (77),
163 (23). HRMS Calcd for C18H18ISe (M + H+): 440.9618.
40 Found: 440.9623.
(CDCl3, 400 MHz): δ 8.57 (d, J = 9.2 Hz, 1H), 8.50-8.41 (m, 3H),
7.64-7.51 (m, 2H), 7.29 (dd, J = 9.0 Hz, J = 2.2 Hz, 1H), 3.99 (s,
3H), 3.02 (t, J = 7.4 Hz, 2H), 1.67 (quint, J = 7.4 Hz, 2H), 1.42
(sex, J = 7.4 Hz, 2H), 0.86 (t, J = 7.4 Hz, 3H). 13C RMN (CDCl3,
95 100 MHz): δ 159.2, 138.5, 136.9, 135.5, 132.6, 131.2, 128.0,
127.1, 127.4, 124.6, 122.2, 120.8, 117.7, 114.2, 55.5, 32.3, 31.2,
23.1, 13.5. MS (EI, 70 eV) m/z (relative intensity): 454 (47), 453
(4), 271 (100), 270 (45), 269 (78), 268 (37), 267 (44), 191 (72),
190 (29), 189 (91), 179 (31). HRMS Calcd for C19H20IOSe (M +
100 H+): 470.9724. Found: 470.9730.
Butyl(10-iodo-7-methylphenanthren-9-yl)selane (2b): Isolated
by column chromatography (hexane and ethyl acetate 99:1 as
eluent) as a yellow solid. Yield: 0.08 g (71%); m.p. 61.4-62.9 ⁰C.
1H NMR (CDCl3, 400 MHz): δ 8.66 (s, 1H), 8.47-8.41 (m, 3H),
45 7.59-7.49 (m, 2H), 7.41 (dd, J = 8.4 Hz, J = 1.6 Hz, 1H), 2.97 (t,
J = 7.4 Hz, 2H), 2.56 (s, 3H), 1.63 (quint, J = 7.4 Hz, 2H), 1.41
(sex, J = 7.4 Hz, 2H), 0.83 (t, J = 7.4 Hz, 3H). 13C RMN (CDCl3,
100 MHz): δ 138.9, 137.6, 136.8, 134.0, 133.2, 132.8, 131.2,
128.9, 128.4, 127.8, 127.6, 122.8, 122.4, 120.1, 32.0, 31.4, 23.0,
50 21.6, 13.5. MS (EI, 70 eV) m/z (relative intensity): 454 (40), 453
(4), 271 (100), 270 (40), 269 (77), 268 (34), 267 (36), 191 (73),
190 (23), 189 (67). HRMS Calcd for C19H20ISe (M + H+):
454.9775. Found: 454.9780.
2'-(Butylselanyl)-3'-iodospiro[cyclohexa[2,5]diene-1,1'-inden]-
4-one (2e’): Isolated by column chromatography (hexane and
ethyl acetate 98:2 as eluent) as a black solid. Yield: 0.06 g (53%);
1
m.p. 84.1-85.6 ⁰C. H NMR (CDCl3, 400 MHz): δ 7.41 (td, J =
105 7.4 Hz, J = 1.0 Hz, 1H), 7.36-7.34 (m, 1H), 7.28-7.23 (m, 1H),
7.07-7.05 (m, 1H), 7.56-7.52 (m, 2H), 6.35-6.32 (m, 2H), 2.92 (t,
J = 7.4 Hz, 2H), 1.62 (quint, J = 7.4 Hz, 2H), 1.38 (sex, J = 7.4
Hz, 2H), 0.82 (t, J = 7.4 Hz, 3H). 13C RMN (CDCl3, 100 MHz): δ
185.7, 146.7, 145.9, 142.5, 141.9, 131.3, 129.2, 127.7, 123.3,
110 110.7, 64.3, 32.3, 28.3, 22.6, 13.4. MS (EI, 70 eV) m/z (relative
intensity): 454 (12), 453 (4), 273 (25), 245 (27), 243 (27), 181
(21), 165 (100), 164 (27), 163 (55), 152 (23). HRMS Calcd for
C18H18IOSe (M + H+): 456.9568. Found: 456.9575.
Butyl(10-iodo-6-methylphenanthren-9-yl)selane and butyl(10-
55 iodo-8-methylphenanthren-9-yl)selane (2c:2c’): Compounds 2c
and 2c’ exist as an inseparable mixture (2c:2c’ / 2.5:1, determined
by H NMR) isolated by column chromatography (hexane and
ethyl acetate 99:1 as eluent) as yellow oil. Total yield: 0.089 g
Butyl(10-iodo-6-methoxyphenanthren-9-yl)selane
115 butyl(10-iodo-8-methoxyphenanthren-9-yl)selane
and
(2f:2f’):
Compounds 2f and 2f’ exist as an inseparable mixture (2f:2f’ /
1
3.3:1, determined by 1H NMR) isolated by column
6
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DOI: 10.1039/C6OB01807F
chromatography (hexane and ethyl acetate 98:2 as eluent) as 60 8.17 (dd, J = 11.4 Hz, J = 2.6 Hz, 1H), 7.46 (ddd, J = 8.4 Hz, J =
yellow oil. Total yield: 0.106 g (90%). The combined chemical
shifts are reported. H NMR (CDCl3, 400 MHz): δ 8.81 (d, J =
9.2 Hz, 1H), 8.50-8.41 (m, 2H), 8.02-7.97 (m, 1H), 7.64-7.54 (m,
3H), 7.27-7.17 (m, 2H), 4.01-3.96 (m, 4H), 2.97 (t, J = 7.4 Hz,
1.8 Hz, J = 0.4 Hz, 1H), 7.31 (ddd, J = 9.1 Hz, J = 7.5 Hz, J = 2.6
Hz, 1H), 2.98 (t, J = 7.4 Hz, 2H), 2.57 (s, 3H), 1.64 (quint, J =
7.4 Hz, 2H), 1.41 (sex, J = 7.4 Hz, 2H), 0.85 (t, J = 7.4 Hz, 3H).
13C RMN (CDCl3, 100 MHz): δ 161.9 (d, J1 = 246.0 Hz, 1C),
1
5
2H), 1.66-1.57 (m, 3H), 1.45-1.34 (m, 3H), 0.89 (t, J = 7.4 Hz, 65 140.5, 137.5, 134.9 (d, J3 = 8.8 Hz, 1C), 133.5, 132.9, 129.3,
0.3H), 0.83 (t, J = 7.4 Hz, 3H). 13C RMN (CDCl3, 100 MHz): δ
158.7, 138.7, 136.8, 135.0, 133.8, 131.8, 130.8, 128.8, 128.2,
127.5, 122.7, 117.3, 116.6, 104.3, 55.5, 32.1, 31.4, 23.1, 13.5. MS
128.0, 127.7 (d, J5 = 2.0 Hz, 1C), 125.0 (d, J3 = 8.8 Hz, 1C),
122.7, 121.5 (d, J2 = 24.4 Hz, 1C), 118.2 (d, J4 = 3.8 Hz, 1C),
116.5 (d, J2 = 23.7 Hz, 1C), 32.1, 31.5, 23.0, 21.6, 13.5. MS (EI,
70 eV) m/z (relative intensity): 473 (10), 472 (54), 470 (27), 416
10 (EI, 70 eV) m/z (relative intensity): 470 (45), 469 (9), 467 (23),
289 (20), 288 (20), 287 (100), 286 (30), 285 (52), 284 (31), 283 70 (22), 289 (100), 288 (34), 287 (73), 286 (30), 285 (34), 209 (31),
(25), 243 (23), 163 (53). HRMS Calcd for C19H20IOSe (M + H+):
470.9724. Found: 470.9739.
207 (38) 57 (30). HRMS Calcd for C19H19FISe (M + H+):
472.9681. Found: 472.9690.
Butyl(6-iodochrysen-5-yl)selane (2g): Isolated by column
(10-Iodo-7-methylphenanthren-9-yl)(phenyl)selane
(2k):
15 chromatography (hexane and ethyl acetate 99:1 as eluent) as a
brown solid. Yield: 0.085 g (70%); m.p. 56.9-59.0 ⁰C. H NMR 75 99:1 as eluent) as a brown solid. Yield: 0.089 g (75%); m.p.
Isolated by column chromatography (hexane and ethyl acetate
1
1
(CDCl3, 400 MHz): δ 9.53-9.51 (m, 1H), 8.55-8.51 (m, 2H),
8.40-8.37 (m, 1H), 7.94 (d, J = 8.9 Hz, 1H), 7.89-7.86 (m, 1H),
7.65-7.60 (m, 2H), 7.57-7.53 (m, 2H), 2.53 (t, J = 7.4 Hz, 2H),
20 1.13 (quint, J = 7.4 Hz, 2H), 0.97 (sex, J = 7.4 Hz, 2H), 0.54 (t, J
125.6-128.2 ⁰C. H NMR (CDCl3, 400 MHz): δ 8.58-8.47 (m,
4H), 7.68-7.64 (m, 1H), 7.60-7.56 (m, 1H), 7.46 (dd, J = 8.4 Hz,
J = 1.8 Hz, 1H), 7.24-7.21 (m, 2H), 7.15-7.08 (m, 3H), 2.16 (s,
3H). 13C RMN (CDCl3, 100 MHz): δ 138.0, 137.1, 133.8, 133.4,
= 7.4 Hz, 3H). 13C RMN (CDCl3, 100 MHz): δ 135.5, 135.0, 80 133.3, 132.7, 131.6, 129.4, 129.3, 129.3, 128.7, 128.3, 127.8,
133.7, 132.7, 130.8, 130.7, 130.1, 129.2, 128.3, 127.9, 127.3,
126.7, 124.6, 123.1, 120.5, 117.5, 33.6, 31.3, 22.5, 13.2. MS (EI,
70 eV) m/z (relative intensity): 490 (6), 307 (65), 306 (100), 305
25 (26), 304 (59), 281 (22), 226 (61), 227 (37). HRMS Calcd for
C22H20ISe (M + H+): 490.9775. Found: 490.9780.
126.1, 122.8, 122.6, 121.1, 21.6. MS (EI, 70 eV) m/z (relative
intensity): 474 (43), 473 (3), 346 (28), 332 (55), 267 (50), 266
(100), 265 (55), 252 (71), 189 (66), 166 (29), 165 (26), 126 (36).
HRMS Calcd for C21H16ISe (M + H+): 474.9462. Found:
85 474.9471.
Butyl(10-iodo-3,7-dimethylphenanthren-9-yl)selane
(2h):
(10-Iodo-7-methylphenanthren-9-yl)(p-tolyl)selane
(2l):
Isolated by column chromatography (hexane and ethyl acetate
99:1 as eluent) as a brown solid. Yield: 0.07 g (60%); m.p. 75.7-
30 76.2 ⁰C. 1H NMR (CDCl3, 400 MHz): δ 8.67 (s, 1H), 8.50 (d, J =
Isolated by column chromatography (hexane and ethyl acetate
99:1 as eluent) as a white solid. Yield: 0.099 g (81%); m.p.
1
146.9-148.8 ⁰C. H NMR (CDCl3, 400 MHz): δ 8.62-8.50 (m,
8.4 Hz, 1H), 8.33-8.31 (m, 2H), 7.46 (d, J = 8.4 Hz, 1H), 7.37 (d, 90 4H), 7.69-7.65 (m, 1H), 7.61-7.57 (m, 1H), 7.46 (dd, J = 8.3 Hz,
J = 7.5 Hz, 1H), 2.98 (t, J = 7.4 Hz, 2H), 2.59 (s, 3H), 2.58 (s,
3H), 1.63 (quint, J = 7.4 Hz, 2H), 1.41 (sex, J = 7.4 Hz, 2H), 0.84
(t, J = 7.4 Hz, 3H). 13C RMN (CDCl3, 100 MHz): δ 137.8, 137.5,
35 136.6, 134.1, 132.7, 131.3, 131.2, 129.3, 128.8, 128.1, 122.9,
J = 1.6 Hz, 1H), 7.15 (d, J = 8.1 Hz, 2H), 6.95 (d, J = 8.0 Hz,
2H), 2.48 (s, 3H), 2.22 (s, 3H). 13C RMN (CDCl3, 100 MHz): δ
138.5, 138.0, 137.1, 136.1, 133.9, 133.4, 132.8, 131.6, 130.1,
129.8, 129.6, 129.2, 128.8, 128.3, 127.8, 122.8, 122.6, 121.0,
122.2, 120.0, 32.0, 31.2, 23.0, 21.7, 21.7, 13.5. MS (EI, 70 eV) 95 21.6, 21.0. MS (EI, 70 eV) m/z (relative intensity): 488 (42), 487
m/z (relative intensity): 468 (46), 467 (4), 285 (100), 284 (55),
283 (79), 282 (52), 281 (45), 270 (26), 205 (34), 203 (30), 202
(55), 189 (43). HRMS Calcd for C20H22ISe(M + H+): 468.9931.
40 Found: 468.9936.
(3), 346 (52), 344 (29), 281 (48), 280 (100), 266 (45), 265 (68),
253 (32), 207 (28), 189 (47), 133 (28). HRMS Calcd for
C22H18ISe (M + H+): 488.9618. Found: 488.9622.
(10-Iodo-7-methylphenanthren-9-yl)(4-methoxyphenyl)selane
100 (2m): Isolated by column chromatography (hexane and ethyl
acetate 97:3 as eluent) as a yellow solid. Yield: 0.097 g (77%);
Butyl(10-iodo-2-methoxy-7-methylphenanthren-9-yl)selane
(2i): Isolated by column chromatography (hexane and ethyl
acetate 97:3 as eluent) as a yellow oil. Yield: 0.099 g (82%). H
1
1
m.p. 84.1-86.3 ⁰C. H NMR (CDCl3, 400 MHz): δ 8.61 (s, 1H),
NMR (CDCl3, 400 MHz): δ 8.62 (s, 1H), 8.39-8.33 (m, 2H), 7.86
45 (d, J = 2.6 Hz, 1H), 7.40 (dd, J = 8.4 Hz, J = 1.4 Hz, 1H), 7.20
(dd, J = 9.0 Hz, J = 2.6 Hz, 1H), 3.95 (s, 3H), 2.97 (t, J = 7.4 Hz,
2H), 2.55 (s, 3H), 1.63 (quint, J = 7.4 Hz, 2H), 1.40 (sex, J = 7.4
Hz, 2H), 0.84 (sex, J = 7.4 Hz, 3H). 13C RMN (CDCl3, 100
MHz): δ 159.0, 139.3, 136.5, 134.5, 132.9, 132.7, 129.0, 138.4,
50 125.4, 124.2, 122.3, 119.6, 118.1, 117.7, 55.4, 32.0, 31.4, 23.0,
21.6, 13.5. MS (EI, 70 eV) m/z (relative intensity): 484 (58), 483
(6), 482 (29), 301 (100), 300 (38), 299 (53), 298 (33), 257 (27),
207 (27), 179 (31), 176 (44). HRMS Calcd for C20H22IOSe (M +
H+): 484.9881. Found: 484.9885.
8.50-8.43 (m, 3H), 7.62-7.57 (m, 1H), 7.55-7.51 (m, 1H), 7.39
(dd, J = 8.4 Hz, J = 1.5 Hz, 1H), 7.25 (d, J = 8.9 Hz, 2H), 6.66 (d,
105 J = 8.9 Hz, 2H), 3.64 (s, 3H), 2.56 (s, 3H). 13C RMN (CDCl3, 100
MHz): δ 158.7, 139.1, 137.8, 137.0, 133.7, 133.3, 132.7, 132.1,
131.5, 129.1, 128.7, 128.1, 127.7, 123.5, 122.8, 122.5, 120.5,
115.1, 52.1, 21.6. MS (EI, 70 eV) m/z (relative intensity): 504 (2),
281 (30), 253 (17), 208 (18), 207 (100), 191 (18), 133 (25), 96
110 (31), 73 (44). HRMS Calcd for C22H18IOSe (M + H+): 504.9568.
Found: 504.9573.
(10-Iodo-7-methylphenanthren-9-yl)(naphthalen-1-yl)selane
(2n): Isolated by column chromatography (hexane and ethyl
acetate 99:1 as eluent) as a yellow solid. Yield: 0.078 g (60%);
55 Butyl(2-fluoro-10-iodo-7-methylphenanthren-9-yl)selane (2j):
Isolated by column chromatography (hexane and ethyl acetate
99:1 as eluent) as a yellow solid. Yield: 0.053 g (45%); m.p.
1
115 m.p. 212.5-214.6 ⁰C. H NMR (CDCl3, 400 MHz): δ 8.59-8.50
(m, 4H), 8.34 (d, J = 8.4 Hz, 1H), 7.82 (d, J = 8.0 Hz, 1H), 7.69-
7.64 (m, 1H), 7.62-7.57 (m, 3H), 7.53-7.49 (m, 1H), 7.44 (d, J =
8.5 Hz, 1H), 7.08-7.01 (m, 2H), 2.33 (s, 3H). 13C RMN (CDCl3,
1
63.5-65.1 ⁰C. H NMR (CDCl3, 400 MHz): δ 8.64-8.63 (m, 1H),
8.49 (dd, J = 9.1 Hz, J = 5.6 Hz, 1H), 8.38 (d, J = 8.5 Hz, 1H),
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100 MHz): δ 138.2, 138.1, 137.1, 134.3, 134.1, 133.6, 132.7,
4H), 7.69-7.64 (m, 1H), 7.62-7.57 (m, 1H), 7.47 (dd, J = 8.4 Hz,
132.5, 132.5, 131.7, 129.4, 128.9, 128.7, 128.4, 127.8, 127.5, 60 J = 0.5 Hz, 1H), 7.17-7.12 (m, 2H), 7.08-7.03 (m, 3H), 2.46 (s,
126.7, 126.4, 126.3, 126.2, 125.8, 122.9, 122.7, 121.0, 21.4.
HRMS Calcd for C25H18ISe (M + H+): 524.9618. Found:
524.9625.
3H). 13C RMN (CDCl3, 100 MHz): δ 138.0, 137.4, 136.5, 136.2,
133.3, 133.2, 131.6, 129.4, 129.4, 129.1, 129.0, 128.5, 127.7,
126.6, 125.4, 122.8, 122.6, 120.9, 21.6. MS (EI, 70 eV) m/z
(relative intensity): 427 (7), 426 (33), 299 (39), 298 (33), 295
65 (14), 285 (22), 284 (100), 189 (15), 149 (18), 148 (15), 142 (44),
141 (20). HRMS Calcd for C21H16IS (M + H+): 427.0017. Found:
427.0023.
5
(4-Fluorophenyl)(10-iodo-7-methylphenanthren-9-yl)selane
(2o): Isolated by column chromatography (hexane and ethyl
acetate 99:1 as eluent) as a yellow solid. Yield: 0.056 g (46%);
1
m.p. 191.5-192.6 ⁰C. H NMR (CDCl3, 400 MHz): δ 8.57-8.47
9,10-Diiodo-2-methylphenanthrene (2t): Isolated by column
10 (m, 4H), 7.67-7.62 (m, 1H), 7.59-7.55 (m, 1H), 7.44 (dd, J = 8.4
chromatography (hexane and ethyl acetate 99:1 as eluent) as a
Hz, J = 1.5 Hz, 1H), 7.26-7.22 (m, 2H), 6.83 (t, J = 8.8 Hz, 2H),
2.48 (s, 3H). 13C RMN (CDCl3, 100 MHz): δ 161.9 (d, J1 = 246.1 70 white solid. Yield: 0.103 g (95%); m.p. 132.4-134.0 ⁰C. 1H NMR
Hz, 1C), 138.4, 138.0, 137.1, 133.7, 133.4, 132.6, 131.8 (d, J3 =
7.7 Hz, 1C), 131.7, 129.3, 128.9, 128.4, 127.9 (d, J4 = 3.6 Hz,
15 1C), 127.8, 133.0, 122.6, 120.8, 116.5 (d, J2 = 21.9 Hz, 1C), 21.5.
MS (EI, 70 eV) m/z (relative intensity): 492 (36), 491 (10), 364
(CDCl3, 400 MHz): δ 7.39-7.29 (m, 4H), 7.25-7.21 (m, 3H), 2.39
(s, 3H). 13C RMN (CDCl3, 100 MHz): δ 145.5, 139.5, 137.3,
137.2, 130.8, 129.2, 129.0, 128.9, 128.9, 128.8, 128.4, 127.3,
126.6, 114.2, 21.3. HRMS Calcd for C15H11I2 (M + H+):
(48), 350 (48), 284 (100), 283 (61), 281 (37), 270 (72), 189 (88), 75 444.8950. Found: 444.8959.
135 (32). HRMS Calcd for C21H15FISe (M + H+): 492.9368.
Found: 492.9371.
General Procedure for the Synthesis of 9-organochalcogen-
phenanthrenes 3: To a solution of aryl disselenide (1.1 equiv) in
dry CH2Cl2 (2 mL), was added FeCl3 (2.0 equiv.). The resulting
solution was stirred at room temperature under argon atmosphere
20 (4-Chlorophenyl)(10-iodo-7-methylphenanthren-9-yl)selane
(2p): Isolated by column chromatography (hexane and ethyl
acetate 99:1 as eluent) as a yellow solid. Yield: 0.051 g (40%); 80 for 15 minutes. After that a solution of aryl (biphenyl-2-ethynyl)
1
m.p. 210.1-212.6 ⁰C. H NMR (CDCl3, 400 MHz): δ 8.61-8.48
(m, 4H), 7.71-7.65 (m, 1H), 7.63-7.57 (m, 1H), 7.49 (dd, J = 8.4
25 Hz, J = 1.8 Hz, 1H), 7.17-7.08 (m, 4H), 2.49 (s, 3H). 13C RMN
(CDCl3, 100 MHz): δ 138.2, 137.8, 137.2, 133.8, 133.5, 132.5,
132.4, 131.7, 130.8, 128.7, 129.5, 129.4, 128.9, 128.5, 127.9,
123.0, 122.7, 121.1, 21.6. MS (EI, 70 eV) m/z (relative intensity):
508 (4), 346 (44), 300 (33), 265 (47), 208 (54), 207 (53), 191
30 (100), 189 (71). HRMS Calcd for C21H15ClISe (M + H+):
508.9072. Found: 508.9079.
1 (0.25 mmol) in CH2Cl2 (1 mL) was added. The resulting
solution was stirred at room temperature until complete
consumption of the starting material. The reaction was quenched
by the addition of a saturated aqueous solution of NH4Cl (5 mL).
85 The mixture was extracted with ethyl acetate (3 x 5 mL) and the
combined organic extracts were dried over MgSO4, filtered and
concentrated in vacuo. The residue was purified by column
chromatography over silica gel using hexane and ethyl acetate as
eluent to provide phenanthrenes 3.
(10-Iodo-7-methylphenanthren-9-yl)(methyl)sulfane
(2q): 90 (2-Methyl-10-phenylphenanthren-9-yl)(phenyl)selane
(3a):
Isolated by column chromatography (hexane and ethyl acetate
99:1 as eluent) as a yellow solid. Yield: 0.098 g (93%); m.p.
Isolated by column chromatography (hexane and ethyl acetate
99:1 as eluent) as a yellow solid. Yield: 0.01 g (55%); m.p. 94.3-
1
1
35 96.2 ⁰C. H NMR (CDCl3, 400 MHz): δ 8.68-8.67 (m, 1H), 8.52
134.4-135.7 ⁰C. H NMR (CDCl3, 400 MHz): δ 8.65 (d, J = 8.3
Hz, 1H), 8.60 (d, J = 8.2 Hz, 1H), 8.55 (d, J = 8.5 Hz, 1H), 7.55-
(d, J = 8.5 Hz, 2H), 8.45-8.42 (m, 1H), 7.64-7.54 (m, 2H), 7.49
(d, J = 8.4 Hz, 1H), 2.60 (s, 3H), 2.43 (s, 3H). 13C RMN (CDCl3, 95 7.35 (m, 6H), 7.23-7.17 (m, 3H), 7.01-6.93 (m, 5H), 2.31 (s, 3H).
13C RMN (CDCl3, 100 MHz): δ 146.5, 142.0, 136.5, 134.3,
100 MHz): δ 139.9, 137.9, 136.2, 133.0, 132.6, 131.2, 129.2,
132.2, 132.1, 130.7, 130.5, 129.6, 129.2, 129.0, 129.0, 128.8,
128.3, 127.9, 127.6, 127.2, 127.1, 126.9, 125.4, 122.5, 122.4,
21.6. MS (EI, 70 eV) m/z (relative intensity): 424 (54), 423 (8),
100 422 (28), 345 (30), 344 (100), 343 (32), 329 (31), 266 (26), 265
(35), 252 (62). HRMS Calcd for C27H21Se (M + H+): 425.0808.
Found: 425.0813.
129.1, 128.7, 128.0, 127.6, 123.0, 122.4, 118.8, 21.7, 19.8. MS
40 (EI, 70 eV) m/z (relative intensity): 265 (17), 244 (93), 223 (19),
222 (100), 221 (54), 189 (30), 178 (21), 111 (25). HRMS Calcd
for C16H14IS (M + H+): 364.9861. Found: 364.9870.
Ethyl(10-iodo-7-methylphenanthren-9-yl)sulfane (2r): Isolated
by column chromatography (hexane and ethyl acetate 99:1 as
45 eluent) as a yellow solid. Yield: 0.061 g (65%); m.p. 84.2-86.4
(2-Methyl-10-phenylphenanthren-9-yl)(p-tolyl)selane
(3b):
1
Isolated by column chromatography (hexane and ethyl acetate
⁰C. H NMR (CDCl3, 400 MHz): δ 8.71-8.70 (m, 1H), 8.56-8.53
105 99:1 as eluent) as a yellow solid. Yield: 0.086 g (79%); m.p.
(m, 2H), 8.47-8.45 (m, 1H), 7.66-7.55 (m, 2H), 7.50 (ddd, J = 8.4
Hz, J = 1.8 Hz, J = 0.5 Hz, 1H), 2.97 (qua, J = 7.4 Hz, 2H), 2.60
(s, 3H), 1.27 (t, J = 7.4 Hz, 3H). 13C RMN (CDCl3, 100 MHz): δ
50 138.7, 137.7, 136.4, 133.3, 133.2, 131.1, 129.5, 129.1, 128.7,
128.0, 127.6, 122.9, 122.5, 119.7, 31.5, 21.7, 14.5. MS (EI, 70
eV) m/z (relative intensity): 379 (20), 378 (100), 223 (67), 222
(63), 221 (50), 189 (27), 179 (40), 178 (29). HRMS Calcd for
C17H16IS (M + H+): 379.0017. Found: 379.0021.
1
53.9-56.5 ⁰C. H NMR (CDCl3, 400 MHz): δ 8.66 (dd, J = 8.4
Hz, J = 1.2 Hz, 2H), 8.63 (d, J = 8.5 Hz, 1H), 7.62-7.58 (m, 1H),
7.52-7.45 (m, 2H), 7.43-7.39 (m, 3H), 7.23-7.19 (m, 3H), 6.92 (d,
J = 8.2 Hz, 2H), 6.84 (d, J = 8.0 Hz, 2H), 2.37 (s, 3H), 2.17 (s,
110 3H). 13C RMN (CDCl3, 100 MHz): δ 146.4, 142.2, 136.5, 135.2,
132.3, 132.3, 130.8, 130.7, 130.5, 129.8, 129.7, 129.4, 129.1,
129.0, 128.3, 128.0, 127.9, 127.2, 127.1, 126.9, 122.5, 122.5,
21.6, 20.0. MS (EI, 70 eV) m/z (relative intensity): 438 (47), 437
(5), 359 (31), 358 (100), 357 (25), 343 (25), 266 (26), 265 (43),
115 263 (29), 252 (68), 91 (45). HRMS Calcd for C28H23Se (M + H+):
439.0965. Found: 439.0969.
55 (10-Iodo-7-methylphenanthren-9-yl)(phenyl)sulfane
(2s):
Isolated by column chromatography (hexane and ethyl acetate
99:1 as eluent) as a yellow solid. Yield: 0.082 g (77%); m.p.
1
145.0-146.6 ⁰C. H NMR (CDCl3, 400 MHz): δ 8.59-8.46 (m,
8
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1
60 0.09 g (79%). H NMR (CDCl3, 400 MHz): δ 8.66 (dd, J = 8.3
Hz, J = 0.9 Hz, 1H), 8.65 (d, J = 8.2 Hz, 1H), 8.60 (d, J = 8.5 Hz,
1H), 7.61-7.57 (m, 1H), 7.51-7.43 (m, 2H), 7.33 (d, J = 8.5 Hz,
2H), 7.19-7.18 (m, 1H), 7.09 (d, J = 8.4 Hz, 2H), 6.98 (s, 5H),
2.36 (s, 3H). 13C RMN (CDCl3, 100 MHz): δ 145.2, 140.4, 136.7,
(4-Fluorophenyl)(2-methyl-10-phenylphenanthren-9-yl)selane
(3c): Isolated by column chromatography (hexane and ethyl
acetate 99:1 as eluent) as a brown solid. Yield: 0.057 g (52%);
1
m.p. 134.9-137.1 ⁰C. H NMR (CDCl3, 400 MHz): δ 8.72-8.63
5
(m, 3H), 7.66-7.61 (m, 1H), 7.56-7.48 (m, 2H), 7.44-7.41 (m,
3H), 7.23-7.17 (m, 3H), 7.00-6.96 (m, 2H), 6.73 (t, J = 8.8 Hz, 65 134.2, 133.2, 133.2, 132.0, 131.1, 130.8, 130.6, 129.3, 129.2,
2H), 2.39 (s, 3H). 13C RMN (CDCl3, 100 MHz): δ 161.3 (d, J1 =
129.0, 128.9, 128.2, 128.1, 128.0, 127.2, 127.2, 125.6, 122.6,
122.5, 21.6. MS (EI, 70 eV) m/z (relative intensity): 458 (51), 456
(22), 378 (100), 342 (29), 266 (45), 265 (79), 263 (55), 207 (40),
163 (43). HRMS Calcd for C27H20ClSe (M + H+): 459.0419.
70 Found: 459.0427.
245.0 Hz, 1C), 146.5, 142.0, 136.7, 132.2, 132.0, 131.2 (d, J3 =
7.5 Hz, 1C), 130.9, 130.4, 129.8, 129.3, 129.0, 128.6 (d, J4 = 3.3
10 Hz, 1C), 128.3, 128.0, 128.0, 127.3, 127.1, 127.0, 122.6, 122.5,
116.0 (d, J2 = 21.5 Hz, 1C), 21.6. MS (EI, 70 eV) m/z (relative
intensity): 442 (53), 441 (8), 440 (27), 363 (29), 362 (100), 347
(28), 266 (25), 265 (39), 263 (27), 252 (65). HRMS Calcd for
C27H20FSe (M + H+): 443.0714. Found: 443.0720.
(10-(4-Chlorophenyl)-2-methylphenanthren-9-yl)(p-
tolyl)selane (3h): Isolated by column chromatography (hexane
and ethyl acetate 99:1 as eluent) as a yellow solid. Yield: 0.095 g
1
(81%); m.p. 56.3-58.4 ⁰C. H NMR (CDCl3, 400 MHz): δ 8.70-
15 (2-Methyl-10-(naphthalen-2-yl)phenanthren-9-
yl)(phenyl)selane (3d): Isolated by column chromatography 75 8.67 (m, 2H), 8.64 (d, J = 8.5 Hz, 1H), 7.65-7.60 (m, 1H), 7.55-
(hexane and ethyl acetate 99:1 as eluent) as a yellow solid. Yield:
0.061 g (52%); m.p. 77.3-79.9 ⁰C. 1H NMR (CDCl3, 400 MHz): δ
8.69 (t, J = 8.5 Hz, 2H), 8.64 (d, J = 8.5 Hz, 1H), 7.87 (t, J = 8.5
20 Hz, 2H), 7.69 (d, J = 8.3 Hz, 1H), 7.63-7.59 (m, 2H), 7.53-7.43
(m, 4H), 7.36 (dd, J = 8.3 Hz, J = 1.5 Hz, 1H), 7.24 (s, 1H), 6.97
(s, 5H), 2.30 (s, 3H). 13C RMN (CDCl3, 100 MHz): δ 146.4,
139.5, 136.7, 134.4, 133.1, 132.6, 132.4, 132.2, 10.8, 130.6,
129.4, 129.2, 129.1, 128.9, 128.6, 128.4, 128.2, 128.2, 127.8,
25 127.5, 127.1, 127.0, 126.1, 125.9, 125.5, 122.6, 122.5, 21.5. MS
7.47 (m, 2H), 7.37 (d, J = 8.5 Hz, 2H), 7.18-7.17 (m, 1H), 7.13
(d, J = 8.5 Hz, 2H), 6.89 (d, J = 8.2 Hz, 2H), 6.85 (d, J = 8.1 Hz,
2H), 2.40 (s, 3H), 2.18 (s, 3H). 13C RMN (CDCl3, 100 MHz): δ
145.1, 140.5, 136.7, 135.4, 133.2, 132.2, 132.1, 131.2, 130.8,
80 130.7, 130.3, 129.8, 129.3, 129.3, 129.0, 128.3, 128.2, 128.0,
127.2, 127.1, 122.6, 122.5, 21.6, 20.9. MS (EI, 70 eV) m/z
(relative intensity): 474 (25), 473 (14), 472 (56), 471 (7), 394
(33), 393 (34), 392 (100), 281 (38), 266 (35), 265 (60), 263 (46),
91 (40). HRMS Calcd for C28H22ClSe (M + H+): 473.0575.
(EI, 70 eV) m/z (relative intensity): 474 (88), 473 (13), 472 (43), 85 Found: 473.0586.
395 (37), 394 (93), 316 (36), 315 (38), 313 (31), 303 (31), 302
(100). HRMS Calcd for C31H23Se (M + H+): 475.0965. Found:
475.0971.
(10-(4-Chlorophenyl)-2-methylphenanthren-9-yl)(4-
fluorophenyl)selane (3i): Isolated by column chromatography
(hexane and ethyl acetate 99:1 as eluent) as a yellow solid. Yield:
0.097 g (82%); m.p. 55.9-56.7 ⁰C. 1H NMR (CDCl3, 400 MHz): δ
30 (2-Methyl-10-(naphthalen-2-yl)phenanthren-9-yl)(p-
tolyl)selane (3e): Isolated by column chromatography (hexane 90 8.70-8.65 (m, 2H), 8.64 (d, J = 8.5 Hz, 1H), 7.66-7.62 (m, 1H),
and ethyl acetate 99:1 as eluent) as a yellow oil. Yield: 0.082 g
(67%). H NMR (CDCl3, 400 MHz): δ 8.73-8.67 (m, 2H), 8.64
(d, J = 8.5 Hz, 1H), 7.92-7.87 (m, 2H), 7.74-7.72 (m, 1H), 7.64-
35 7.61 (m, 2H), 7.55-7.46 (m, 4H), 7.36 (dd, J = 8.3 Hz, J = 1.6 Hz,
7.60-7.53 (m, 1H), 7.50 (dd, J = 8.5 Hz, J = 1.5 Hz, 1H), 7.39 (d,
J = 8.5 Hz, 2H), 7.19-7.18 (m, 1H), 7.10 (d, J = 8.5 Hz, 2H),
6.98-6.93 (m, 2H), 6.73 (t, J = 8.8 Hz, 2H), 2.39 (s, 3H). 13C
RMN (CDCl3, 100 MHz): δ 161.5 (d, J1 = 245.6 Hz, 1C), 145.1,
1
1H), 7.24-7.20 (m, 1H), 6.88 (d, J = 8.2 Hz, 2H), 6.80 (d, J = 8.0 95 140.3, 136.9, 133.3, 132.0 (d, J4 = 2.0 Hz, 1C), 131.3 (d, J3 = 7.8
Hz, 2H), 2.31 (s, 3H), 2.17 (s, 3H). 13C RMN (CDCl3, 100 MHz):
δ 146.2, 139.5, 136.6, 135.3, 133.1, 132.6, 132.4, 132.3, 130.8,
130.7, 130.5, 129.7, 129.6, 129.2, 129.0, 128.7, 128.5, 128.3,
40 128.3, 128.2, 127.8, 127.5, 127.1, 126.9, 126.0, 125.9, 122.6,
Hz, 1C), 131.2, 130.9, 130.4, 129.4, 129.1, 128.4, 128.1, 128.2,
128.0, 127.3, 122.7, 122.6, 116.1 (d, J2 = 21.7 Hz, 1C), 21.6. MS
(EI, 70 eV) m/z (relative intensity): 478 (17), 476 (56), 396 (100),
281 (60), 266 (35), 265 (69), 263 (55), 207 (33), 96 (48), 73 (39).
122.5, 21.5, 20.9. HRMS Calcd for C32H25Se (M + H+): 100 HRMS Calcd for C27H19ClFSe (M + H+): 477.0325. Found:
489.1121. Found: 489.1127.
477.0331.
(4-Fluorophenyl)(2-methyl-10-(naphthalen-2-yl)phenanthren-
(2-Methoxy-10-phenylphenanthren-9-yl)(phenyl)selane (3j):
9-yl)selane (3f): Isolated by column chromatography (hexane
Isolated by column chromatography (hexane and ethyl acetate
45 and ethyl acetate 99:1 as eluent) as a yellow oil. Yield: 0.06 g
(49%). H NMR (CDCl3, 400 MHz): δ 8.71 (d, J = 8.3 Hz, 2H), 105 159.4-161.3 ⁰C. H NMR (CDCl3, 400 MHz): δ 8.66-8.57 (m,
98:2 as eluent) as a yellow solid. Yield: 0.108 g (99%); m.p.
1
1
8.66 (d, J = 8.5 Hz, 1H), 7.93-7.88 (m,2H), 7.75-7.71 (m, 1H),
7.67-7.63 (m, 1H), 7.58-7.47 (m, 5H), 7.33 (dd, J = 8.3 Hz, J =
1.7 Hz, 1H), 7.24-7.23 (m, 1H), 6.95-6.90 (m, 2H), 6.68 (t, J =
50 8.8 Hz, 2H), 2.32 (s, 3H). 13C RMN (CDCl3, 100 MHz): δ 161.4
(d, J1 = 245.1 Hz, 1C), 146.2, 139.3, 136.8, 133.1, 132.6, 132.3,
132.1, 151.5 (d, J3 = 7.5 Hz, 1C), 130.9, 130.4, 129.3, 129.0,
128.7, 128.6 (d, J4 = 3.4 Hz, 1C), 128.5, 128.3, 128.2, 127.8,
127.5, 127.2, 127.1, 126.2, 126.0, 122.6, 122.6, 116.0 (d, J2 =
55 21.8 Hz, 1C), 21.5. HRMS Calcd for C31H22FSe (M + H+):
493.0871. Found: 493.0879.
3H), 7.60-7.56 (m, 1H), 7.48-7.44 (m, 1H), 7.39-7.38 (m, 3H),
7.25 (dd, J = 9.1 Hz, J = 2.7 Hz, 1H), 7.22-7.19 (m, 2H), 7.02-
6.98 (m, 5H), 6.82 (d, J = 2.7 Hz, 1H), 3.64 (s, 3H). 13C RMN
(CDCl3, 100 MHz): δ 158.1, 164.2, 142.0, 134.3, 133.6, 131.4,
110 130.8, 130.6, 129.6, 129.2, 129.9, 128.2, 128.0, 127.3, 127.1,
126.5, 125.5, 124.2, 122.2, 117.3, 109.8, 55.1. MS (EI, 70 eV)
m/z (relative intensity): 441 (21), 440 (73), 438 (38), 361 (31),
360 (100), 268 (16), 252 (20), 240 (20), 239 (65). HRMS Calcd
for C27H21OSe (M + H+): 441.0758. Found: 441.0765.
115 (2-Chloro-10-phenylphenanthren-9-yl)(phenyl)selane
(3k):
(10-(4-Chlorophenyl)-2-methylphenanthren-9-
yl)(phenyl)selane (3g): Isolated by column chromatography
(hexane and ethyl acetate 99:1 as eluent) as a yellow oil. Yield:
Isolated by column chromatography (hexane and ethyl acetate
99:1 as eluent) as a yellow solid. Yield: 0.102 g (92%); m.p.
162.5-163.8 ⁰C. 1H NMR (CDCl3, 400 MHz): δ 8.68 (dd, J = 8.3
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Hz, J = 1.3 Hz, 1H), 8.62-8.60 (m, 2H), 7.64-7.60 (m, 1H), 7.58- 60 122.3, 97.5, 90.3, 32.6, 29.8, 22.9, 21.7, 13.4. HRMS Calcd for
7.51 (m, 2H), 7.42-7.37 (m, 4H), 7.19-7.17 (s, 5H). 13C RMN
(CDCl3, 100 MHz): δ 145.7, 141.2, 133.9, 133.2, 132.7, 132.4,
130.8, 130.2, 129.6, 129.4, 129.4, 129.3, 129.0, 128.1, 127.8,
127.8, 127.6, 127.4, 125.7, 124.2, 122.6. MS (EI, 70 eV) m/z
(relative intensity): 446 (40), 445 (25), 444 (85), 442 (42), 366
(36), 365 (32), 364 (100), 330 (28), 329 (47), 328 (58), 252 (91),
250 (60). HRMS Calcd for C26H18ClSe (M + H+): 445.0262.
Found: 445.0278.
C27H24ClSe (M + H+): 463.0732. Found: 463.0740.
3-Iodo-10-methyl-2-phenylphenanthro[9,10-b]selenophene
(6a): Isolated by column chromatography (hexane and ethyl
acetate 99:1 as eluent) as a yellow solid. Yield: 0.088 g (71%);
65 m.p. 130.9-133.5 ⁰C. 1H NMR (CDCl3, 400 MHz): δ 10.06-10.02
(m, 1H), 8.70-8.66 (m, 1H), 8.53 (d, J = 8.5 Hz, 1H), 7.69-7.63
(m, 3H), 7.59-7.56 (m, 2H), 7.51-7.43 (m, 4H), 2.55 (s, 3H). 13C
RMN (CDCl3, 100 MHz): δ 145.8, 142.6, 138.8, 137.4, 133.5,
130.6, 130.3, 129.4, 129.3, 129.0, 128.6, 128.4, 126.1, 125.2,
70 125.2, 124.1, 123.3, 123.3, 78.8, 21.5. MS (EI, 70 eV) m/z
(relative intensity): 498 (100), 372 (78), 370 (47), 356 (88), 354
(40), 289 (53), 281 (89), 276 (47), 207 (50), 138 (41), 73 (41).
HRMS Calcd for C23H16ISe (M + H+): 498.9462. Found:
498.9470.
5
10 (2-Methyl-10-phenylphenanthren-9-yl)(phenyl)sulfane
(3l):
Isolated by column chromatography (hexane and ethyl acetate
1
99:1 as eluent) as a yellow oil. Yield: 0.024 g (26%). H NMR
(CDCl3, 400 MHz): δ 8.70 (d, J = 8.3 Hz, 1H), 8.64 (d, J = 8.5
Hz, 1H), 8.59 (dd, J = 8.3 Hz, J = 0.9 Hz, 1H), 7.66-7.60 (m, 1H),
15 7.55-7.48 (m, 2H), 7.41-7.38 (m, 3H), 7.24-7.20 (m, 3H), 7.06-
7.01 (m, 2H), 6.98-6.94 (m, 1H), 6.89-6.86 (m, 2H), 2.39 (s, 3H).
13C RMN (CDCl3, 100 MHz): δ 146.6, 140.3, 139.1, 136.6, 75 2-(4-Chlorophenyl)-3-iodo-10-methylphenanthro[9,10-
132.4, 131.8, 131.0, 129.5, 129.4, 129.0, 128.6, 128.2, 128.0,
127.9, 127.3, 127.2, 127.1, 127.0, 126.4, 124.6, 122.5, 21.6. MS
20 (EI, 70 eV) m/z (relative intensity): 377 (27), 376 (100), 343 (15),
284 (28), 282 (9), 265 (17), 263 (9), 252 (22), 207 (14). HRMS
Calcd for C27H21S (M + H+): 377.1364. Found: 377.1372.
b]selenophene (6b): Isolated by column chromatography
(hexane and ethyl acetate 99:1 as eluent) as a yellow solid. Yield:
0.089 g (67%); m.p. 189.2-191.3 ⁰C. 1H NMR (CDCl3, 400
MHz): δ 10.02-9.99 (m, 1H), 8.68-8.66 (m, 1H), 8.51 (d, J = 8.4
80 Hz, 1H), 7.67-7.63 (m, 3H), 7.51-7.44 (m, 5H), 2.55 (s, 3H). 13C
RMN (CDCl3, 100 MHz): δ 144.3, 142.9, 137.6, 137.4, 134.9,
133.6, 131.9, 130.5, 129.4, 129.3, 129.1, 128.7, 126.4, 126.3,
125.3, 125.3, 124.1, 123.3, 79.2, 21.4. HRMS Calcd for
C23H15ClISe (M + H+): 532.9072. Found: 532.9081.
(10-(4-Chlorophenyl)-2-methylphenanthren-9-
yl)(phenyl)sulfane (3m): Isolated by column chromatography
25 (hexane and ethyl acetate 99:1 as eluent) as a yellow oil. Yield:
0.038 g (37%). 1H NMR (CDCl3, 400 MHz): δ 8.72-8.70 (m,
1H), 8.65 (d, J = 8.5 Hz, 1H), 8.61 (ddd, J = 8.3 Hz, J = 1.3 Hz, J
= 0.5 Hz, 1H), 7.67-7.62 (m, 1H), 7.56-7.50 (m, 2H), 7.36 (d, J =
8.6 Hz, 2H), 7.21-7.20 (m, 1H), 7.13 (d, J = 8.6 Hz, 2H), 7.07-
30 6.95 (m, 3H), 6.87-6.84 (m, 2H), 2.41 (s, 3H). 13C RMN (CDCl3,
100 MHz): δ 145.3, 138.9, 138.7, 136.8, 133.3, 132.1, 131.8,
131.0, 129.5, 129.1, 128.7, 128.2, 128.0, 127.9, 127.5, 127.2,
127.2, 126.4, 124.8, 122.7, 122.6, 21.6. MS (EI, 70 eV) m/z
(relative intensity): 412 (40), 411 (30), 410 (100), 345 (15), 342
35 (16), 298 (31), 297 (17), 295 (19), 266 (17), 265 (27), 263 (26).
HRMS Calcd for C27H20ClS (M + H+): 411.0974. Found:
411.0982.
85
Acknowledgments
We are grateful to FAPERGS, CAPES and CNPq for the
financial support. CNPq is also acknowledged for the fellowships
(T. B. G and G. Z.).
90 Notes and references
a
Laboratório de Síntese, Reatividade, Avaliação Farmacológica
e
Toxicológica de Organocalcogênios, CCNE, UFSM, Santa Maria ꢀ Rio
Grande do Sul – Brasil ꢀ 97105ꢀ900.
Butyl(7-methyl-10-(phenylethynyl)phenanthren-9-yl)selane
(5a): Isolated by column chromatography (hexane and ethyl
40 acetate 99:1 as eluent) as a yellow oil. Yield: 0.192 g (90%). H
b Laboratório de Materiais Inorgânicos, CCNE, UFSM, Santa Maria, Rio
95 Grande do Sul, Brazil, 97105ꢀ900.
1
† Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/b000000x/
NMR (CDCl3, 400 MHz): δ 8.69-8.42 (m, 4H), 7.78-7.55 (m,
4H), 7.51-7.31 (m, 4H), 3.08 (t, J = 7.3 Hz, 2H), 2.58 (s, 3H),
1.73-1.56 (m, 2H), 1.49-1.32 (m, 2H), 0.80 (t, J = 7.3 Hz, 3H).
13C RMN (CDCl3, 100 MHz): δ 137.1, 133.5, 133.3, 131.6,
45 131.0, 130.3, 130.2, 129.1, 128.4, 128.1, 127.6, 127.5, 127.3,
126.8, 123.7, 122.8, 122.4, 98.8, 89.3, 32.6, 29.7, 22.9, 21.7,
13.5. MS (EI, 70 eV) m/z (relative intensity): 428 (100), 427 (14),
426 (52), 372 (70), 371 (45), 370 (50), 369 (42), 356 (64), 292
(73), 289 (58), 276 (54). HRMS Calcd for C27H25Se (M + H+):
50 429.1121. Found: 429.1123.
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