3-Aryl Substituted 1-Methylquinolinium Salts as Carbene Precursors

Article abstract of DOI:10.1002/ejoc.201801648

1-Methylquinolinium salts substituted at the C3 position with phenyl, naphthalen-1-yl, phenanthren-9-yl, and pentaphenyl phenyl as well as aryl ethynyl substituents were prepared. The phenyl, naphthalen-1-yl, and phenanthren-9-yl substituents are in conjugation with the quinolinium ring, and the sterically crowded pentaphenyl phenyl residue causes a propeller-type molecule possessing a calculated dihedral angle between aryl substituent and the quinolinium ring of approximately 54°. The different influences of the substituents including the aryl ethynyl residues on the π-architecture is well reflected in their frontier orbital profiles, their spectroscopic properties, and in their ability to form N-heterocyclic carbenes. The latter were generated from the C3-aryl substituted quinolinium salts and trapped as sulfur and selenium adducts, whereas the aryl ethynyl substituted derivatives failed to undergo the NHC generation under the conditions applied. ⁷⁷Se NMR measurements of the corresponding selenones reveal that quinolin-2-ylidenes are electron poor carbenes with strong π-acceptor character.

Full text of DOI:10.1002/ejoc.201801648

A Journal of
Accepted Article
Title: 3-Aryl Substituted 1-Methylquinolinium Salts as Carbene
Precursors
Authors: Sviatoslav Batsyts, Roman Vedmid, Jan C. Namyslo, Martin
Nieger, and Andreas Schmidt
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201801648
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10.1002/ejoc.201801648
European Journal of Organic Chemistry
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3-Aryl Substituted 1-Methylquinolinium Salts as Carbene
Precursors
Sviatoslav Batsyts,[a] Roman Vedmid,[a] Jan C. Namyslo,[a] Martin Nieger,[b] and Andreas Schmidt*[a]
Abstract: 1-Methylquinolinium salts substituted at the C3 position
with phenyl, naphthalen-1-yl, phenanthren-9-yl, and pentaphenyl
phenyl as well as aryl ethynyl substituents were prepared. Whereas
the phenyl, naphthalen-1-yl and phenanthren-9-yl substituents are in
conjugation with the quinolinium ring, the sterically crowded
pentaphenyl phenyl residue causes
a propeller-type molecule
possessing a calculated dihedral angle between aryl substituent and
the quinolinium ring of approximately 54°. The different influences of
the substituents including the aryl ethynyl residues on the -
architecture is well reflected in their frontier orbital profiles, their
spectroscopic properties and in their ability to form N-heterocyclic
carbenes. The latter were generated from the C3-aryl substituted
quinolinium salts and trapped as sulfur and selenium adducts,
whereas the aryl ethynyl substituted derivatives failed to undergo the
NHC generation under the conditions applied. 77Se NMR
measurements of the corresponding selenones reveal that quinolin-2-
ylidenes are electron poor carbenes with strong -acceptor character.
Introduction
Scheme 1. Preparative routes for the synthesis of NHCs I from cyclic precursors.
The first stable carbene A was described by Bertrand et al. in
1988[1]. Although a strong multiple-bond character of the P-C
bond stabilizes A, it can react as a carbene species (Scheme 1).
Three years later, Arduengo et al.[2] reported on the N-heterocyclic
carbene B which was synthesized by deprotonation of 1,3-di-1-
adamantylimidazolium chloride with sodium hydride. Meanwhile a
great variety of sterically and electronically diverse carbenes have
been reported.[3] Nowadays, NHCs are used as starting materials
for heterocycle synthesis,[4] as highly efficient ligands for metal-
catalyzed reactions,[5] and as organocatalysts.[6] Several synthetic
procedures to generate NHCs I from cyclic precursors such as
heterocumulene adducts II, hetarenium salts III, partially
saturated systems IV, mesomeric betaines V, and thiones VI are
known.[7] In comparison to the widely applied and structurally
diverse five-membered NHCs, the chemistry of six-membered
NHCs is less explored. Pyridin-2-ylidene 1, proposed as a
reactive intermediate of the Hammick reaction[8] as early as 1937,
was later identified by mass spectroscopy combined with
computational quantum chemistry[9] (Scheme 2).
Palladium complexes of pyridin-2-ylidene 1 and pyridin-4-ylidene
2 as well as of their related quinolines were prepared from the
corresponding chlorohetarenium salts and Pd(PPh3)4 by oxidative
addition and, furthermore, they were screened for their catalytic
activities.[10] Other transition metal complexes such as nickel,[11]
osmium,[12] and iridium[13] complexes have been described as well.
Several trapping reactions of these carbenes have been
performed.[14] Pyridin-4-ylidene 2 can be classified as remote
NHC and can be drawn with an electron sextet structure in
analogy to normal NHCs, whereas pyridin-3-ylidene, another
remote NHC, can only be presented by dipolar structure 3. The
pyrazin-2-ylidene 4 was formed by decarboxylation of pyrazinium-
2-carboxylate[15] as precursor which is a pseudo-cross-conjugated
mesomeric betaine (PCCMB). Mass spectrometric examinations
have been performed.[16] Phthalazine can form a carbene
complex with palladium by insertion into chlorophthalazine. This
enables the formation of phthalazine derivatives of 5.[17,18]
[a]
S. Batsyts, R. Vedmid, Dr. J. C Namyslo, Prof. Dr. A. Schmidt
Clausthal University of Technology, Institute of Organic Chemistry,
Leibnizstrasse 6, D-38678 Clausthal-Zellerfeld (Germany)
Fax:(+ 49)-5323-722834
E-mail: schmidt@ioc.tu-clausthal.de
http://www.ioc.tu-clausthal.de
Scheme 2. Six-membered N-heterocyclic carbenes.
[b]
Dr. M. Nieger
University of Helsinki,
Department of Chemistry
P. O. Box 55 (A.I. Virtasen aukio 1), 00014 Helsinki (Finland)
The pyridinium salt precursors of the NHCs 1, 2, and 3 possess a
reduced electron density at position 2/6 and 4 as evidenced by
the mesomeric structures of N-methylpyridinium (Scheme 3). The
total electron deficiency was calculated to be +0.165 (C4) and
Supporting information for this article is given via a link at the end of
the document.
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10.1002/ejoc.201801648
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+0.241 (C2/6), respectively.[19] The lowest unoccupied molecular
orbital (LUMO) resembles ψ4* of benzene. Its polarization,
however, causes a considerably larger coefficient at C4 than at
C2/6.[20] Quinolinium salts show similar properties.
acetylenes 7 and 3-bromoquinoline 6, followed by methylation.
Compound 8d was converted into 8g by a Diels-Alder reaction
with pentaphenylcyclopentenone. Methylation employing the
aforementioned method gave the quinolinium derivative 9g in
almost quantitative yields. Due to mutual repulsion and steric
hindrance of the side wings the molecule has to adopt a propeller-
type conformation.
Scheme 3. Total electron deficiency, resonance structures, and the LUMO of
N-methylpyridinium.
To the best of our knowledge stable quinolinium carbenes are not
known, and only
a few carbene complexes have been
synthesized so far.[10, 21] Some examples are given in Scheme 4.
Scheme 4. Quinoline carbene complexes.
In continuation of our interest in the different types of conjugation
and their consequences for N-heterocyclic carbene formation[7, 22]
we examined the influence of substituents at C3 of quinolinium on
trapping reactions of quinolin-2-ylidenes generated from them.
We chose different aryl and ethynyl substituents which are in
conjugation to the quinolinium ring. These are, in summary, slight
electron donators in terms of Hammett´s substituent constants
(Ph: m +0.06, p -0.01; -C≡C-Ph: m +0.14, p +0.16).[23] However,
they cause different -architectures of the quinolinium salts which
take influence of the spectroscopic properties as well as on the
chemistry of the compounds in terms of NHC generation.
Scheme 5. Synthesis of 3-substituted quinolines 8a-f by cross-coupling
reactions and 1-methyl-3-substituted quinolinium methylsulfates 9a-g.
Different 13C NMR resonance frequencies of C3 of the quinolinium
ring are observed. Whereas the 3-aryl substituted quinolinium
salts 9a-c and 9g show chemical shifts of their C3 carbon atom
between 133.4 ppm and 134.4 ppm, the 3-ethynyl substituted
compounds show signals between 116.2 and 116.8 ppm.
Correspondingly, the natural charges at C3 were calculated to be
-0.067 (9a), -0.129 (9d) and -0.063 (9g) [B3LYP 6-31G(d,p)]. All
other data of calculated NMR shifts as well as natural charges of
the model compounds 9a, 9d and 9g are presented in the
supplementary material. We also calculated the most stable
conformations and frontier orbitals. The dihedral angle between
benzene and quinoline rings in salt 9a was calculated to be 37.9°
in vacuo. The corresponding angle in the propeller-type salt 9g is
larger and has a value of 54.1°. The five other phenyl rings are
twisted from 66° to 68° with respect to the central phenyl ring. In
the ethynyl substituted salt 9d the two aromatics are planar with
respect to each other. The calculated C3-CAr bond lengths in 9a
Results and Discussion
Syntheses of 3-substituted quinolinium salts
To prepare the starting compounds, 3-bromoquinoline 6 was
subjected to a Suzuki-Miyaura reaction with aryl boronic acids in
the presence of 10% Pd(CH3COO)2 as a catalyst and K3PO4 as a
base in toluene/water solution to give 3-aryl quinolines 8a-c
(Scheme 5). Related to previous works,[22c,24] dimethyl sulfate was
used as a convenient reagent for the quaternization of 8a-c to give
the salts 9a-c in high yields. 50 l of nitrobenzene were used as
a catalyst in these reactions. The syntheses of the 3-alkynyl
substituted quinolinium salts 9d-f were accomplished by
Sonogashira coupling reactions with the corresponding
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10.1002/ejoc.201801648
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and 9g is comparable and adopt values of 148.0 pm and 149.4
pm, respectively. The calculated C3-Csp bond length of 9d is
shorter with a value of 141.2 pm. The HOMO/LUMO profiles are
shown in Figure 1. The coefficients of the lowest unoccupied
molecular orbital (LUMO) of 9a and 9g are exclusively located in
the quinolinium ring. In salt 9d a small LUMO coefficient is also
located on the C carbon atom of the C≡C triple bond. The HOMO
of the propeller-type salt 9g is strictly separated from the LUMO´s
coefficients and is located on the opposite side of the molecule.
Coefficients of the HOMOs of 9a and 9d are distributed in the
entire molecules with their highest coefficients in the substituents
at C3. The calculated band gaps have values of 3.36, 2.24, and
2.67 eV for 9a, 9g, and 9d, respectively.
Scheme 6. The reaction of salt 9cPF6 with LiHMDS in [D8]THF and
characteristic chemical shifts.
Next we performed a series of reactions to deprotonate the
quinolinium salt 9c at C2 in the presence of elemental sulfur and
to form thiones as trapping products of the corresponding N-
heterocyclic carbenes. Lithium hydroxide gave no reaction
(Scheme 7, A). Potassium tert-butoxide[25] in anhydrous toluene
under reflux conditions gave the quinolinone 10, presumably
formed by addition of the base at C2 followed by thermal
elimination of isobutene. The C2 carbon atom of 10 gives the
signal at 162.0 ppm in the 13C NMR spectrum. Interaction of 9c
and potassium tert-pentoxide in acetonitrile has been examined
by HRMS. The electrospray ionization mass shows the molecular
peak at m/z = 374.0948, which corresponds to the potassium
adduct 10.K+. The addition of LiOH did not improve the yield
(Scheme 7, B and C). However, using potassium tert-pentoxide
led to a color change during the reaction and gave thione 11c as
an orange solid in 20% yield. Addition of 1.2 equiv of potassium
tert-pentoxide and 10 equiv of LiOH increased the yield to 90%.
Exchanging LiOH to LiBr also led to an increased yield 11c
compared to conditions without lithium compounds. However,
potassium tert-pentoxide proved vital as LiOH alone did not give
successful results as described above (Scheme 7, D-F).
Figure 1. HOMO (left) and LUMO (right) profiles of carbene precursors 9g
(above), 9a (middle), and 9d (below).
NHC formations and trapping reactions
First, deprotonations of the quinolinium salts were examined by
base screenings in combination with NMR experiments. To
increase the solubility of the salt 9c, which is insoluble in toluene
or benzene, the methylsulfate anion was exchanged to
hexafluorophosphate by precipitation in aqueous solution.
Addition of potassium tert-pentoxide or LiHMDS to a solution of
salt 9c in [D6]DMSO, [D8]THF or [D3]MeCN at room temperature
led to an upfield shift of the resonance frequencies, however,
considerable amounts of decomposition products were visible in
the spectra. By contrast, the base LiHMDS in [D8]THF formed the
adduct 13 of the electrophilic iminium moiety of 9cPF6 (Scheme
6).
Scheme 7. Trapping reaction of salt 9c with sulfur under different conditions.
Applying the optimized reaction condition to 9a,b,g gave the
corresponding thiones 11a,b,g as orange colored solids, however,
in lower yields (Scheme 8). The same conditions for the
generation of NHCs and their trapping with sulfur have been
applied to the 3-ethynyl substituted quinolinium salts 9d-f,
however, without results. No reaction occurred.
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Whereas the 13C chemical shifts of the C2 atoms of the selenones
12a-c are very close to the C2 carbon atoms of the thiones 11a-
c, the resonance frequencies of methyl groups differ significantly
(c.f. supplementary material). The structure of 12c was proven by
X-ray structure analysis (Figure 3). Single crystals of selenone
12c were obtained by diffusion of cyclohexane into its solution in
chloroform. The compound crystallized monoclinic. The C=Se
bond has a length of 183.8(2) pm. The typical C(sp2)=Se double
bond length is 171 pm[27] and the typical C(sp2)-Se single bond
length is 189 pm[26]. The dihedral angle between the quinoline and
naphthalene planes is 70.08(3)°.
Scheme 8. Trapping reactions of NHCs generated from the salts 9a-c and 9g
with sulfur by optimized conditions.
The resonance frequencies of the C=S carbon atoms in CDCl3 are
shifted downfield compared to the C=O signal of 10 and adopt
values of 185.0, 185.4, and 185.3 ppm, respectively. The
structure of 11b was additionally proven by X-ray structure
analysis (Figure 2). Single crystals of thione 11b were obtained
by slow evaporation of a concentrated solution in chloroform. The
compound crystallized orthorhombic. The CS bond has a length
of 168.39(18) pm. The typical C(sp2)=S double bond length is in
the range from 159.9 to 161.1 pm, whereas the C(sp2)-S single
bond length is 177 pm.[26] The dihedral angle between the
quinoline and naphthalene planes is 77.56(3)°.
Figure 3. Molecular structure of selenone 12c (displacement parameters are
drawn at 50% probability level).
Quinoline selenones are rare and little information is available.
Only a few compounds have been described so far.[28] The 77Se
NMR spectra for 12a-c were measured and the signals of Se
atoms were found at 706.6, 716.8, and 720.4 ppm, respectively.
These downfield shifts indicate electron poor former carbenes
with strong -acceptor character (Scheme 10).[29] The 77Se
chemical shift of 1-methylquinoline-2(1H)-selenone has a value of
646.7 ppm.[28c]
Figure 2. Molecular structure of thione 11b (displacement parameters are
drawn at 50% probability level).
Reactions of the 3-substituted quinolinium salts 9a-c with
elemental selenium in the presence of potassium tert-pentoxide
gave the selenones 12a-c (Scheme 9). All selenones are red
compounds with a specific odor. Furthermore, the bulkier the
aromatic substituent, the higher the melting point in thiones and
selenones. Thus, the selenone with a phenanthrenyl residue
(12c) has a melting point of 271 °C, while the selenone with a
phenyl residue (12a) is an oil.
Scheme 10. Comparison of Ganter’s NHC selenium adducts. 77Se chemical
shifts of 12a-c.
Conclusions
Aryl as well as ethynyl substituents at position 3 of quinolinium
salts were prepared. Whereas the former mentioned underwent
trapping reactions of their N-heterocyclic carbenes with sulfur and
selenium, respectively, the latter failed to undergo these reactions.
This work supplements results concerning the electrophilicities vs.
acidities in six-membered N-heterocyclic carbene precursors.[30]
Scheme 9. Trapping reactions of salts 9a-c with selenium.
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10.1002/ejoc.201801648
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Intel® CoreTM i7-6950X deca core system equipped with 64 GB RAM main
memory and sufficient solid-state disc space. MMFF optimized structures
were used as starting geometries. Then, the B3LYP density functional and
the 6-31G(d,p) basis set was used in order to allow for comparison with
previous results. All final structures were proven to be true minima by the
absence of imaginary frequencies or transition states by the occurrence of
a negative frequency.
Experimental Section
All reactions were carried out under an atmosphere of nitrogen in flame or
oven-dried glassware. All chemicals were purchased and used without
further purification unless otherwise mentioned. Anhydrous solvents were
dried according to standard procedures before usage. Melting points are
uncorrected and were determined in an apparatus according to Dr. Tottoli
(Büchi). The ATR-IR spectra were obtained on a Bruker Alpha in the range
of 400 to 4000 cm-1. 1H NMR spectra were recorded at 400 MHz or 600
MHz. 13C NMR spectra were recorded at 100 MHz or 150 MHz, with the
solvent peak used as the internal reference. Multiplicities are described by
using the following abbreviations: s = singlet, d = doublet, t = triplet, q =
quartet, and m = multiplet. Signal orientations in DEPT experiments were
described as follows: o = no signal; + = up (CH, CH3); - = down (CH2). 77Se
NMR spectra were recorded at 114 MHz. The electrospray ionization mass
spectra (ESIMS) were measured with a Varian 320 MS Triple Quad
GC/MS/MS (EIMS) or with an Agilent LCMSD series HP 1100 with APIES
at fragmentor voltages as indicated. Samples were sprayed from MeOH at
4000 V capillary voltage and fragmentor voltages of 30 V unless otherwise
noted. The HR-MS spectra were obtained with a Bruker Impact II, a Bruker
Daltonik Tesla-Fourier transform-ion cyclotron resonance mass
spectrometer, or with a Waters Micromass LCT with the direct inlet.
Chromatography: The reactions were traced by thin layer chromatography
with silica gel 60 (F254, company MERCK KGAA). For the detection of
substances, quenching was used at either 254 nm or 366 nm with a
mercury lamp. The preparative column chromatography was conducted
through silica gel 60 (230 400 mesh) of the company MERCK KGAA.
General procedure for the preparation of the 3-arylquinolines
(Procedure 1; Suzuki-Miyaura coupling): Under a nitrogen atmosphere,
1.040 g (5.00 mmol) of 3-bromoquinoline 6 were dissolved in 20 mL of
anhydrous toluene unless otherwise noted and treated with 10-mol-% of
Pd(CH3COO)2 The mixtures were then subjected to ultrasound irradiation
for 5 min and then stirred at rt for additional 0.5 h. Then 6.00 mmol of the
boronic acid, 40.00 mmol of potassium phosphate and 4 mL of water were
added, and the mixtures were heated under reflux for 24 h. The mixtures
were then allowed to cool to rt, treated with dichloromethane (50 mL) and
washed with water. The organic phases were then dried over MgSO4 and
filtered, and the solvents were removed in vacuo. The resulting residues
were finally purified by column chromatography (petroleum ether: ethyl
acetate) to afford the products.
3-Phenylquinoline (8a): According to Procedure 1, a solution of 1.040 g
(5.00 mmol) of 3-bromoquinoline 6, 0.112 g (0.50 mmol) of Pd(CH3COO)2,
0.732 g (6.00 mmol) phenylboronic acid and 8.480 g (40.00 mmol) of
K3PO4 in 54 mL of the toluene-water mixture was heated for 24 h under
reflux temperature. Finally, a purification by column chromatography
(petroleum ether: ethyl acetate = 3:1) gave 3-phenylquinoline 8a. Yield
0.820 g, 80%, a brownish solid, m.p. 50-51 °C. 1H NMR (600 MHz, CDCl3):
δ = 9.20 (s, 1H, 2-H), 8.31 (d, J = 1.8 Hz, 1H, 4-H), 8.16 (d, J = 8.3 Hz, 1H,
8-H), 7.89 ( d, J = 8.1 Hz, 1H, 5-H), 7.74–7.71 (m, 3H, 7-H, 2ʹ-H, 6ʹ-H),
7.58 (t, J = 7.4 Hz, 1H, 6-H), 7.54–7.52 (m, 2H, 3ʹ-H, 5ʹ-H), 7.44 (m, 1H,
4ʹ-H) ppm. 13C NMR (150 MHz, CDCl3): δ = 150.0 (+, C2), 147.4 (o, C8a),
138.0 (o, C1ʹ), 134.0 (o, C3), 133.4 (+, C4), 129.5 (+, C7), 129.3 (o, C4a),
129.3 (+, C8, C3ʹ, C5ʹ), 128.3 (+, C4ʹ), 128.2 (+, C5), 127.6 (+, C2ʹ, C6ʹ),
127.2 (+, C6) ppm. IR (ATR): 3027, 1568, 1492, 1368, 1340, 1027, 952,
914, 861, 785, 773, 762, 693, 624, 612, 560, 545, 494, 479, 443 cm-1.
Spectroscopic data are in agreement with those reported in the
literature.[33]
Crystal Structure Determinations of 11b and 12c
The single-crystal X-ray diffraction studies were carried out on a Bruker D8
Venture diffractometer with Photon100 detector at 123(2) K using Cu-K
radiation ( = 1.54178 Å. Direct Methods (SHELXS-97)[31] were used for
structure solution and refinement was carried out using SHELXL-2014
(full-matrix least-squares on F2)[32]. Hydrogen atoms were localized by
difference electron density determination and refined using a riding model.
Semi-empirical absorption corrections were applied. 11c was refined as
an inversion twin (see cif-file for details).
11b: yellow crystals, C20H15NS, Mr = 301.39, crystal size 0.20 × 0.18 ×
0.10 mm, orthorhombic, space group P212121 (no. 19), a = 8.3590(5) Å, b
= 12.9270(7) Å, c = 13.7331(7) Å, V = 1483.95(14) Å3, Z = 4, ρ = 1.349
Mg/m-3, µ(Cu-Kα) = 1.874 mm-1, F(000) = 632, 2max = 144.2°, 10197
reflections, of which 2906 were independent (Rint = 0.021), 201 parameters,
R1 = 0.026 (for 2872 I > 2σ(I)), wR2 = 0.072 (all data), S = 1.05, largest diff.
peak / hole = 0.157 / -0.214 e Å-3, x = 0.494(18).
3-(Naphthalen-1-yl)quinoline (8b): According to Procedure 1, a solution
of 1.040 g (5.00 mmol) of 3-bromoquinoline 6, 0.112 g (0.50 mmol) of
Pd(CH3COO)2, 1.032 g (6.00 mmol) naphthalene-1-boronic acid and 8.480
g (40.00 mmol) of K3PO4 in 54 mL of the toluene-water mixture was heated
for 24 h under reflux temperature. Finally, a purification by column
chromatography (petroleum ether: ethyl acetate
= 3:1) gave 3-
(naphthalen-1-yl)quinoline 8b. Yield 1.071 g, 84%, a white solid, m.p. 57-
58 °C. 1H NMR (600 MHz, CDCl3): δ = 9.08 (d, J = 1.9 Hz, 1H, 2-H), 8.28
(d, J = 1.9 Hz, 1H, 4-H), 8.23 (d, J = 8.5 Hz, 1H, 8-H), 7.97 (m, 1H, 5ʹ-H),
7.95 (m, 1H, 4ʹ-H), 7.90 (d, J = 7.9 Hz, 1H, 5-H), 7.87 (d, J = 8.5 Hz, 1H,
8ʹ-H) 7.79 (ddd, J = 1.4, 7.0, 8.4 Hz, 1H, 7-H), 7.63 (ddd, J = 1.0, 7.0, 8.0
Hz, 1H, 6-H), 7.60 (dd, J = 7.0, 8.2 Hz, 1H, 3ʹ-H), 7.54 (ddd, J = 1.2, 6.7,
8.0 Hz, 1H, 6ʹ-H), 7.53 (dd, J = 1.2, 7.0 Hz, 1H, 2ʹ-H), 7.47 (ddd, J = 1.4,
6.9, 8.4 Hz, 1H, 7ʹ-H) ppm. 13C NMR (150 MHz, CDCl3): δ = 152.0 (+, C2),
147.4 (o. C8a), 136.5 (+, C4), 136.4 (o, C1ʹ), 134.0 (o, C4aʹ), 133.9 (o, C3),
131.8 (o, C8aʹ), 129.8 (+, C7), 129.4 (+, C8), 128.8 (+, C4ʹ), 128.7 (+, C5ʹ),
128.1 (+, C5), 128.0 (o, C4a), 127.9 (+, C2ʹ), 127.2 (+, C6), 126.8 (+, C7ʹ),
126.3 (+, C6ʹ), 125.6 (+, C3ʹ), 125.5 (+, C8ʹ) ppm. IR (ATR): 3034, 1811,
1566, 1508, 1490, 1396, 1364, 1332, 1125, 1017, 941, 904, 861, 774, 745,
664, 616, 566, 479, 450, 430 cm-1. Spectroscopic data are in agreement
with those reported in the literature.[34]
12c: red crystals, C24H17NSe, Mr = 398.34, crystal size 0.22 × 0.06 × 0.02
mm, monoclinic, space group P21/c (no. 14), a = 6.1638(2) Å, b =
19.9050(6) Å, c = 14.3978(4) Å, β = 95.257(1)°, V = 1759.04(9) Å3, Z = 4,
ρ = 1.504 Mg/m-3, µ(Cu-Kα) = 2.920 mm-1, F(000) = 808, 2max = 144.2°,
16462 reflections, of which 3473 were independent (Rint = 0.033), 236
parameters, R1 = 0.031 (for 3138 I > 2σ(I)), wR2 = 0.082 (all data), S =
1.05, largest diff. peak / hole = 0.437 / -0.366 e Å-3.
CCDC 1874495 (11b), and 1874496 (12c) contain the supplementary
crystallographic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
Calculations: All density-functional theory (DFT)-calculations were
carried out by using the Spartan® Software (Spartan’16, Wavefunction,
Inc., Irvine, CA. Available from: http://www.wavefun.com) running on an
3-(Phenanthren-9-yl)quinoline (8c): According to Procedure 1, a solution
of 1.040 g (5.00 mmol) of 3-bromoquinoline 6, 0.112 g (0.50 mmol) of
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Pd(CH3COO)2, 1.332 g (6.00 mmol) phenanthrene-9-boronic acid and
8.480 g (40.00 mmol) of K3PO4 in 54 mL of the toluene-water mixture was
heated for 24 h under reflux temperature. Finally, a purification by column
953, 905, 855, 767, 742, 697, 480 cm-1. Spectroscopic data are in
agreement with those reported in the literature.[24]
chromatography (petroleum ether: ethyl acetate
= 3:1) gave 3-
Methyl 2-(quinolin-3-ylethynyl)benzoate (8f): According to Procedure 2,
a solution of 2.080 g (10.00 mmol) of 3-bromoquinoline 6, 0.070 g (0.10
mmol) of Pd(PPh3)2Cl2, 0.038 g (0.20 mmol) CuI and 1.680 g (10.50 mmol)
of methyl 2-ethynylbenzoate in 30 mL of anhydrous NEt3 was heated over
the period of 1.5 h under reflux temperature. Finally, a purification by
column chromatography (petroleum ether: ethyl acetate = 3:1) gave Yield
1.607 g, 56%, a light brownish solid, m.p. 64-65 °C. 1H NMR (600 MHz,
CDCl3): δ = 9.05 (d, J = 2.0 Hz, 1H, 2-H), 8.36 (d, J = 2.0 Hz, 1H, 4-H),
8.11 (d, J = 8.6 Hz, 1H, 8-H), 8.02 (dd, J = 1.5, 7.8 Hz, 1H, 6ʹ-H), 7.81 (d,
J = 8.6 Hz, 1H, 5-H), 7.76-7.69 (m, 2H, 3ʹ-H, 7-H), 7.60–7.50 (m, 2H, 4ʹ-H,
(phenanthren-9-yl)quinoline 8c. Yield 1.068 g, 70%, a light-yellow oil. 1H
NMR (400 MHz, CDCl3): δ = 9.12-9.11 (m, 1H), 8.82-8.80 (m, 1H), 8.76-
8.74 (m, 1H), 8.32-8.31 (m, 1H), 8.24-8.23 (m, 1H), 7.94-7.89 (m, 2H),
7.88-7.86 (m, 1H), 7.81-7.79 (m, 1H), 7.78-7.77 (m, 1H), 7.72-7.69 (m, 2H),
7.66-7.61 (m, 2H), 7.57-7.54 (m, 1H) ppm. 13C NMR (100 MHz, CDCl3): δ
= 152.1, 147.6, 136.4, 135.1, 133.9, 132.4, 131.0, 130.9, 130.4, 129.8,
129.5, 128.9, 128.9, 128.1, 128.0, 127.3, 127.2, 127.2, 127.0, 127.0, 126.5,
123.3, 122.8 ppm. IR (ATR): 3058, 1732, 1618, 1566, 1489, 1449, 1337,
1239, 1123, 1044, 914, 891, 861, 787, 743, 723, 616, 537, 511, 479, 427,
411 cm-1. Spectroscopic data are in agreement with those reported in the
literature.[35]
6-H), 7.42 (td, J = 1.3, 7.8 Hz, 1H, 5ʹ-H), 3.99 (s, 3H, COOCH3) ppm. 13
C
NMR (150 MHz, CDCl3): δ = 166.5 (o, COO), 152.2 (+, C2), 147.0 (o, C8a),
138.5 (+, C4), 134.2 (+, C5ʹ), 131.9 (o, C2ʹ), 131.8 (+, C3ʹ), 130.7 (+, C4ʹ),
130.2(+, C8), 129.5 (+, C6ʹ), 128.5 (+, C7), 127.7 (+, C5), 127.4 (+, C6),
127.3 (C4a), 123.1 (o, C1ʹ), 117.5 (o, C3), 91.5 (o, Cβ), 91.4 (o, Cα), 52.3
(+, CH3) ppm. IR (ATR): 2952, 1731, 1565, 1485, 1435, 1270, 1250, 1111,
1076, 899, 746, 692, 471 cm-1. Spectroscopic data are in agreement with
those reported in the literature.[24]
General procedure of the Sonogashira-Hagihara couplings
(Procedure 2)
The reactions were carried out under a nitrogen atmosphere. A mixture of
5 mmol of 3-bromoquinoline 6, 1 mol % of Pd(PPh3)2Cl2, and 2 mol % of
CuI was suspended in 7 mL of dry NEt3 with stirring. A sample of the
corresponding ethyne 7 (1.05 equiv) in dry NEt3 was added dropwise at
ambient temperature. The resulting solutions were then stirred at reflux
temperature until complete conversion was monitored by TLC. The
mixtures were then allowed to cool to rt. The solvents were removed in
vacuo. The resulting residues were finally purified by column
chromatography (petroleum ether: ethyl acetate) to afford the products.
2,3,4,5,6-Pentaphenyl-1-(quinoline-3-yl)benzene (8g): Benzophenone
(10 g) was melted in a 50 mL round-bottomed flask fitted with an air
condenser. Corresponding 3-(phenylethynyl)quinoline 8d (0.458 g, 2.00
mmol) and tetraphenylcyclopentadienone (0.961 g, 2.50 mmol) were
added to the flask, which was heated for 0.5 h using a heat gun. The
solution was cooled to rt and toluene (10 mL) was added to prevent the
solidification of the benzophenone. After cooling, n-hexane (50 mL) was
added, resulting in the precipitation of a product, which was collected by
vacuum filtration. Yield 0.590 g, 51%, a white solid, m.p. 334-336 °C. 1H
NMR (600 MHz, CDCl3): δ = 8.45 (d, J = 2 Hz, 1H, 2i-H), 7.84 (d, J = 8.4
Hz, 1H, 8i-H), 7.59 (d, J = 2 Hz, 1H, 4i-H), 7.53-7.51 (m, 1H, 7i-H), 7.43 (d,
J = 8.0 Hz, 5i-H), 7.35-7.33 (m, 1H, 6i-H), 6.88-6.85 (m, 20H, 2ii-H, 6ii-H,
2iii-H, 6iii-H, 2iv-H, 6iv-H, 2v-H, 6v-H, 2vi-H, 6vi-H, 3ii-H, 5ii-H, 3iii-H, 5iii-H, 3iv-
H, 5iv-H, 3v-H, 5v-H, 3vi-H, 5vi-H), 6.83-6.78 (m, 4H, 4ii-H, 4iii-H, 4v-H, 4vi-H),
6.78-6.77 (m, 1H, 4iv-H) ppm. 13C NMR (150 MHz, CDCl3): δ = 152.9 (+,
C2i), 145.6 (o, C8ai), 141.4 (o, C4), 141.07 (o, C2, C6), 140.88 (o, C3, C5),
140.44 (o, C1iv), 140.34 (o, C1ii, C1vi), 139.96 (o, C1iii, C1v), 137.8 (+, C4i),
136.51 (o, C1), 134.2 (o, C3i), 131.51/131.48/131.45/131.41/131.37 (+,
C2ii, C6ii, C2iii, C6iii, C2iv, C6iv, C2v, C6v, C2vi, C6vi), 129.0 (+, C8i), 128.9
(+, C7i), 127.6 (+, C5i), 127.4/127.0/126.85/126.83/126.78 (+, C3ii, C5ii,
C3iii, C5iii, C3iv, C5iv, C3v, C5v, C3vi, C5vi), 127.1 (o, C4ai), 126.2 (+, C6i),
125.87 (+, C4ii, C4vi), 125.54 (+, C4iii, C4v), 125.52 (+, C4iv) ppm. IR (ATR):
3055, 3024, 1662, 1600, 1495, 1440, 1401, 1354, 1311, 1275, 1261, 1127,
1070, 1029, 966, 906, 838, 817, 779, 747, 738, 719, 695, 647, 638, 555,
544, 535, 480, 443, 413 cm-1. HRMS (APCI): m/z calcd for C45H32N [M+H]+
586.2529, found 586.2530.
3-(Phenylethynyl)quinoline (8d): According to Procedure 2, a solution of
2.080 g (10.00 mmol) of 3-bromoquinoline 6, 0.070 g (0.10 mmol) of
Pd(PPh3)2Cl2, 0.038 g (0.20 mmol) CuI and 1.071 g (10.50 mmol) of
phenylacetylene in 30 mL of anhydrous NEt3 was heated over the period
of 1.5 h under reflux temperature. Finally, a purification by column
chromatography (petroleum ether: ethyl acetate = 3:1) gave 3-(phenyl-
ethynyl)quinoline 8d. Yield 2.290 g, 100%, a white solid, m.p. 83-84 °C. 1H
NMR (600 MHz, CDCl3): δ = 9.00 (d, J = 2.0 Hz, 1H, 2-H), 8.30 (d, J = 2.0
Hz, 1H, 4-H), 8.10 (d, J = 8.3 Hz, 1H, 8-H), 7.79 (d, J = 8.3 Hz, 1H, 5-H),
7.72 (ddd, J = 1.5, 6.9, 8.3 Hz, 1H, 7-H), 7.63-7.53 (m, 3H, 6-H, 2ʹ-H, 6ʹ-
H), 7.42-7.35 (m, 3H, 3ʹ-H, 4ʹ-H, 5ʹ-H) ppm. 13C NMR (150 MHz, CDCl3): δ
= 152.1 (+, C2), 146.8 (o, C8a), 138.3 (+, C4), 131.8 (+, C2ʹ, C6ʹ), 130.1
(+, C7), 129.4 (+, C8), 128.9 (+, C4ʹ), 128.5 (+, C3ʹ, C5ʹ), 127.6 (+, C6),
127.3 (+, C5), 127.3 (o, C4a), 122.6 (o, C1ʹ), 117.5 (o, C3), 92.7 (o, C),
86.7 (o, C) ppm. IR (ATR): 3008, 2162, 1619, 1599, 1564, 1484, 1443,
1409, 1368, 1294, 1196, 1124, 1113, 1072, 980, 905, 860, 784, 756, 691,
656, 640, 539, 515, 498, 474, 429 cm-1. HRMS (ESI): m/z calcd for
C17H11NNa [M+Na]+ 252.0789, found 252.0796.
Methyl 4-(quinolin-3-ylethynyl)benzoate (8e): According to Procedure 2,
a solution of 2.080 g (10.00 mmol) of 3-bromoquinoline 6, 0.070 g (0.10
mmol) of Pd(PPh3)2Cl2, 0.038 g (0.20 mmol) CuI and 1.680 g (10.50 mmol)
of methyl 4-ethynylbenzoate in 30 mL of anhydrous NEt3 was heated over
the period of 1.5 h under reflux temperature. Finally, a purification by
column chromatography (petroleum ether: ethyl acetate = 3:1) gave Yield
2.153 g, 85%, a brown solid, m.p. 138-139 °C. 1H NMR (600 MHz, CDCl3):
δ = 9.00 (d, J = 2.2 Hz, 1H, 2-H), 8.33 (d, J = 2.2 Hz, 1H, 4-H), 8.11 (d, J
= 8.6 Hz, 1H, 8-H), 8.06 (ddd, J = 1.4, 2.0, 8.3 Hz, 2H, 3ʹ-H, 5ʹ-H), 7.81 (d,
J = 8.6 Hz, 1H, 5-H), 7.74 (ddd, J = 1.5, 6.8, 8.6 Hz, 1H, 7-H), 7.65 (ddd,
J = 1.4, 2.0, 8.3 Hz, 2H, 2ʹ-H, 4ʹ-H), 7.58 (ddd, J = 1.5, 6.8, 8.6 Hz, 1H, 6-
H), 3.94 (s, 3H, COOCH3) ppm. 13C NMR (150 MHz, CDCl3): δ = 166.5 (o,
COO), 152.0 (+, C2), 147.0 (o, C8a), 138.7 (+, C4), 131.7 (+, C2ʹ, C4ʹ),
130.4 (+, C8), 130.0 (o, C4ʹ), 129.7 (+, C3ʹ, C5ʹ), 129.5 (+, C7), 127.7 (+,
C5), 127.5 (+, C6), 127.3 (o, C4a), 127.2 (o, C1ʹ), 116.9 (o, C3), 91.8 (o,
Cβ), 89.5 (o, Cα), 52.3 (+, CH3) ppm. IR (ATR): 3017, 1716, 1276, 1098,
General procedure for the preparation of the salts (Procedure 3):
Samples of 0.50 mmol of the corresponding esters were dissolved in
toluene containing 50 l of nitrobenzene. Then 0.75 mmol of dimethyl
sulfate was added with stirring. Thereafter the resulting mixture was stirred
under reflux temperature. After completion of the reaction (controlled by
TLC), the solution was cooled, the crude product was filtered off, washed
with ethyl acetate (3 × 10 mL), and dried to afford the product.
1-Methyl-3-phenylquinolinium methylsulfate (9a): According to
Procedure 3, a solution of 0.513 g (2.50 mmol) of 3-phenylquinoline, 50 l
drop of nitrobenzene and 0.284 mL (3.00 mmol) of dimethyl sulfate in 15
mL of anhydrous toluene was heated for 2 h under reflux temperature to
give 1-methyl-3-phenylquinolinium methylsulfate 9a. Yield 0.796 g, 96%, a
yellow solid, m.p. 211-212 °C. 1H NMR (600 MHz, [D6]DMSO): δ = 9.96 (d,
J = 1.4 Hz, 1H, 2-H), 9.62 (d, J = 1.4 Hz, 1H, 4-H), 8.53 (d, J = 8.9 Hz, 1H,
This article is protected by copyright. All rights reserved.

10.1002/ejoc.201801648
European Journal of Organic Chemistry
FULL PAPER
8-H), 8.49 (d, J = 8.9 Hz, 1H, 5-H), 8.27 (ddd, J = 1.5, 7.1, 8.9 Hz, 1H, 7-
H), 8.08 (ddd, J = 1.5, 7.1, 8.9 Hz, 1H, 6-H), 8.04–8.03 (m, 2H, 2ʹ-H, 6ʹ-H),
7.66 (t, 2H, J = 7.62 Hz, 3ʹ-H, 5ʹ-H), 7.60–7.58 (m, 1H, 4ʹ-H), 4.72 (s, 3H,
NCH3), 3.37 (s, 3H, CH3SO4) ppm. 13C NMR (150 MHz, [D6]DMSO): δ =
149.3 (+, C2), 142.9 (+, C4), 137.2 (o, C8a), 135.2 (+, C7), 133.5 (o, C3),
133.4 (o, C1ʹ), 130.5 (+, C5), 130.2 (+, C6), 129.8 (+, C4ʹ), 129.5 (+, C3ʹ,
C5ʹ), 129.2 (o, C4a), 127.4 (+, C2ʹ, C6ʹ), 119.0 (+, C8), 52.8 (+, CH3SO4),
45.4 (+, NCH3) ppm. IR (ATR): 3052, 1534, 1504, 1362, 1206, 1051, 1006,
859, 773, 733, 695, 607, 576, 496, 457, 427 cm-1. MS (ESI): m/z = 220.1
[M]+. HRMS (ESI): m/z calcd for C16H14N [M]+ 220.1121, found 220.1126.
(m, 2H), 7.72 (ddd, J = 1.0, 7.0, 7.9 Hz, 1H), 7.67 (ddd, J = 1.2, 6.9, 8.2
Hz, 1H) 4.65 (s, 3H, NCH3) ppm. 13C NMR (150 MHz, CD3CN): δ = 151.7
(+), 148.3 (+), 139.0 (o), 136.9 (+), 135.2 (o), 131.9 (o), 131.8 (o), 131.62
(+), 131.60 (o), 131.58 (+), 131.5 (+), 131.3 (+), 130.64 (o), 130.63 (o),
130.2 (+), 129.2 (+), 128.65 (+), 128.61 (+), 128.60 (+), 126.7 (+), 124.6
(+), 124.6 (+), 123.9 (+), 119.6 (+), 46.6 (+) ppm. IR (ATR): 3053, 1525,
1447, 1378, 1354, 1247, 1214, 1172, 1060, 1012, 901, 825, 746, 724, 658,
608, 577, 551, 490, 427 cm-1. HRMS (ESI): m/z calcd for C24H18N [M]+
320.1434, found 320.1440.
1-Methyl-3-(phenylethynyl)quinolinium methylsulfate (9d): According
1-Methyl-3-(naphthalen-1-yl)quinolinium
methylsulfate
(9b):
to Procedure 3,
a
solution of 1.145
g
(5.00 mmol) of 3-
According to Procedure 3, a solution of 0.638 g (2.50 mmol) of 3-
(naphthalen-1-yl)quinoline, 50 l drop of nitrobenzene and 0.284 mL (3.00
mmol) of dimethyl sulfate in 15 mL of anhydrous toluene was heated for 2
(phenylethynyl)quinoline 8d, 1 drop of nitrobenzene and 0.711 mL (7.50
mmol) of dimethyl sulfate in 25 mL of anhydrous toluene was heated over
the period of 1.5
h under reflux temperature to give 1-methyl-3-
h
under reflux temperature to give 1-methyl-3-(naphthalen-1-
(phenylethynyl)quinolinium methyl-sulfate 9d. Yield 1.757 g, 99%, a yellow
solid, m.p. 224-225 °C (decomp.). 1H NMR (600 MHz, [D6]DMSO): δ = 9.87
(s, 1H, 2-H), 9.50 (s, 1H, 4-H), 8.54 (d, J = 8.8 Hz, 1H, 8-H), 8.45 (d, J =
8.8 Hz, 1H, 5-H), 8.31 (ddd, J = 1.3, 7.1, 8.8 Hz, 1H, 7-H), 8.10 (t, J = 8.8
Hz, 1H, 6-H), 7.74-7.66 (m, 2H, 2ʹ-H, 6ʹ-H), 7.60-7.50 (m, 3H, 3ʹ-H, 4ʹ-H,
5ʹ-H), 4.66 (s, 3H, NCH3), 3.38 (s, 3H, CH3SO4) ppm. 13C NMR (150 MHz,
[D6]DMSO): δ = 153.1 (+, C2), 147.9 (+, C4), 137.3 (o, C8a), 136.0 (+, C7),
131.7 (+, C2ʹ, C6ʹ), 130.6 (+, C4ʹ), 130.3 (+, C6), 130.2 (+, C5), 129.1 (+,
C3ʹ, C5ʹ), 128.7 (o, C4a), 120.5 (o, C1ʹ), 119.2 (+, C8), 116.7 (o, C3), 94.8
(o, C), 83.3 (o, C), 52.8 (+, CH3SO4), 45.4 (+, NCH3) ppm. IR (ATR):
3043, 2941, 2223, 1631, 1606, 1578, 1520, 1493, 1494, 1444, 1365, 1227,
1210, 1173, 1140, 1059, 1010, 929, 910, 878, 766, 737, 695, 607, 577,
552, 524, 501, 479, 429 cm-1. MS (ESI): m/z = 244.1 [M]+. HRMS (ESI):
m/z calcd for C18H14N [M]+ 244.1121, found 244.1126.
yl)quinolinium methylsulfate 9b. Yield 0.916 g, 96%, a yellow solid, m.p.
219-220 °C. 1H NMR (600 MHz, [D6]DMSO): δ = 9.82 (d, J = 1.3 Hz, 1H,
2-H), 9.47 (s, 1H, 4-H), 8.61 (d, J = 8.9 Hz, 1H, 8-H), 8.54 (d, J = 8.2 Hz,
1H, 5-H), 8.35 (ddd, J = 1.5, 7.2, 8.8 Hz, 1H, 7-H), 8.19 (t, J = 4.7 Hz, 1H,
3ʹ-H), 8.15–8.12 (m, 2H, 6-H, 5ʹ-H), 7.95 (d, J = 8.4 Hz, 1H, 8ʹ-H), 7.76–
7.75 (m, 2H, 2ʹ-H, 4ʹ-H), 7.67 (ddd, J = 1.2, 6.9, 8.1 Hz, 1H, 6ʹ-H), 7.62
(ddd, J = 1.2, 6.9, 8.1 Hz, 1H, 7ʹ-H), 4.73 (s, 1H, NCH3), 3.36 (s, 3H,
CH3SO4) ppm. 13C NMR (150 MHz, [D6]DMSO): δ = 151.1 (+, C2), 146.6
(+, C4), 137.5 (o, C8a), 135.4 (+, C7), 133.4 (o, C3), 132.3 (o, C1ʹ), 130.6
(o, C8aʹ), 130.5 (+, C5), 130.2 (+, C6), 129.9 (+, C3ʹ), 129.2 (+, C4a), 128.9
(+, C4ʹ), 128.6 (+, C5ʹ), 127.5 (+, C7ʹ), 126.7 (+, C6ʹ), 125.7 (+, C2ʹ), 124.7
(+, C8ʹ), 119.0 (+, C8), 52.8 (+, CH3SO4), 45.3 (+, NCH3) ppm. IR (ATR):
3041, 2935, 2829, 1524, 1383, 1247, 1215, 1060, 1011, 807, 774, 738,
650, 609, 579, 576, 551, 483, 433 cm-1. MS (ESI): m/z = 270.1 [M]+. HRMS
(ESI): m/z calcd for C20H16N [M]+ 270.1283, found 270.1285.
3-((4-(Methoxycarbonyl)phenyl)ethynyl)-1-methylquinolinium
methylsulfate (9e): According to Procedure 3, a solution of 1.435 g (5.00
mmol) of methyl 4-(quinolin-3-ylethynyl)benzoate 8e, 50 l of nitrobenzene
and 0.711 mL (7.50 mmol) of dimethyl sulfate in 25 mL of anhydrous
toluene was heated for 1.5 h under reflux temperature to give 3-((4-
(methoxycarbonyl)phenyl)ethynyl)-1-methylquinolinium methylsulfate 9e.
Yield 2.044 g, 99%, a brownish solid, m.p. 219-220 °C. 1H NMR (600 MHz,
[D6]DMSO): δ = 9.91 (d, J = 1.2 Hz, 1H, 2-H), 9.54 (d, J = 1.2 Hz, 1H, 4-
H), 8.55 (d, J = 9.0 Hz, 1H, 8-H), 8.46 (d, J = 9.0 Hz, 1H, 5-H), 8.33 (ddd,
J =1.3, 7.0, 9.0 Hz, 1H, 6-H), 8.14–8.07 (m, 3H, 7-H, 2ʹ-H, 6ʹ-H), 7.83 (ddd,
J = 1.5, 1.9, 8.2 Hz, 2H, 3ʹ-H, 5ʹ-H), 4.66 (s, 3H, NCH3), 3.90 (s, 3H,
COOCH3), 3.37 (s, 3H, CH3SO4) ppm. 13C NMR (150 MHz, [D6]DMSO): δ
= 165.5 (o, COO), 152.2 (+, C2), 148.3 (+, C4), 137.5 (o, C8a), 136.3 (+,
C7), 132.1 (+, C2ʹ, C6ʹ), 130.7 (+, C6), 130.5 (o, C4a), 130.4 (+, C5), 129.7
(+, C3ʹ, C5ʹ), 128.7 (o, C4ʹ), 125.2 (C1ʹ), 119.3 (+, C8), 116.2 (o, C3), 93.5
(o, Cα), 85.9 (o, Cβ), 52.8 (+, CH3SO4), 52.5 (+, COOCH3), 45.5 (+, NCH3)
ppm. IR (ATR): 1721, 1278, 1240, 1215, 1170, 1097, 1057, 1005, 866, 766,
729, 696, 607, 574 cm-1. Spectroscopic data are in agreement with those
reported in the literature.[24]
1-Methyl-3-(phenanthren-9-yl)quinolinium
methylsulfate
(9c):
According to Procedure 3, a solution of 0.638 g (2.50 mmol) of 3-
(phenanthren-9-yl)quinoline, 50 l of nitrobenzene and 0.284 mL (3.00
mmol) of dimethyl sulfate in 15 mL of anhydrous toluene was heated for 2
h
under reflux temperature to give 1-methyl-3-(phenanthren-9-
yl)quinolinium methylsulfate 9c. Yield 1.046 g, 97%, a yellow solid, m.p.
209-210 °C. 1H NMR (600 MHz, [D6]DMSO): δ = 9.89 (d, J = 1.1 Hz, 1 H,
2-H), 9.54 (s, 1H, 4-H), 9.05 (d, J = 8.3 Hz, 1H, 5ʹ-H), 8.98 (d, J = 8.2 Hz,
1H, 4ʹ-H), 8.63 (d, J = 9.2 Hz, 1H, 8-H), 8,56 (d, J = 8.2 Hz, 1H, 5-H), 8.37
(ddd, J = 1.5, 7.2, 8.8 Hz, 1H, 7-H), 8.16-8.11 (m, 3H, 6-H, 1ʹ-H, 10ʹ-H)
7.98 (d, J = 7.6 Hz, 1H, 8ʹ-H), 7.86-7.83 (m, 2H, 3ʹ-H, 6ʹ-H), 7.78 (m, 1H,
2ʹ-H), 7.71 (ddd, J = 0.9, 7.2, 8.0 Hz, 1H, 7ʹ-H), 4.74 (s, 3H, NCH3), 3.36
(s, 3H, CH3SO4) ppm. 13C NMR (150 MHz, [D6]DMSO): δ = 151.1 (+, C2),
146.7 (+, C4), 137.7 (o, C8a), 135.5 (+, C7), 133.5 (o, C3), 131.1 (o, C9ʹ),
130.6 (o, C10aʹ), 130.5 (+, C5), 130.2 (+, C6), 130.2 (o, C4bʹ), 130.1 (o,
C4aʹ), 130.0 (+, C10 ʹ), 129.5 (o, C8aʹ), 129.2 (o, C4a), 129.1 (+, C1ʹ),
128.2 (+, C3ʹ), 127.7 (+, C2ʹ), 127.6 (+, C7ʹ), 127.6 (+, C6ʹ), 125.9 (+, C8ʹ),
123.7 (+, C5), 123.1 (+, C4ʹ), 119.0 (+, C8), 52.8 (+, CH3SO4), 45.3 (+,
NCH3) ppm. IR (ATR): 3042, 2944, 1627, 1607, 1578, 1525, 1495, 1447,
1378, 1316, 1217, 1059, 1010, 900, 825, 726, 657, 608, 577, 426 cm-1.
HRMS (ESI): m/z calcd for C24H18N [M]+ 320.1434, found 320.1435.
3-((2-(Methoxycarbonyl)phenyl)ethynyl)-1-methylquinolinium
methylsulfate (9f): According to Procedure 3, a solution of 1.435 g (5.00
mmol) of methyl 2-(quinolin-3-ylethynyl)benzoate 8f, 50 l of nitrobenzene
and 0.711 mL (7.50 mmol) of dimethyl sulfate in 25 mL of anhydrous
toluene was heated for 1.5 h under reflux temperature to give 3-((2-
(methoxycarbonyl)phenyl)ethynyl)-1-methylquinolinium methylsulfate 9f.
Yield 2.044 g, 99%, a yellow solid, m.p. 217-218 °C. 1H NMR (600 MHz,
[D6]DMSO): δ = 9.80 (d, J = 1.0 Hz, 1H, 2-H), 9.47 (d, J = 1.0 Hz, 1H, 4-
H), 8.54 (d, J = 9.1 Hz, 1H, 8-H), 8.50 (d, J = 9.1 Hz, 1H, 5-H), 8.32 (ddd,
J = 1.5, 7.1, 9.1 Hz, 1H, 6-H), 8.11 (ddd, J = 1.5, 7.1, 9.1 Hz, 1H, 7-H),
8.04 (dd, J = 1.0, 8.0 Hz, 1H, 6ʹ-H), 7.85 (dd, J = 1.0, 8.0 Hz, 1H, 3ʹ-H),
7.76 (td, J = 1.5, 7.6 Hz, 1H, 4ʹ-H), 7.66 (td, J = 1.5, 7.6 Hz, 1H, 5ʹ-H), 4.66
(s, 3H, NCH3), 3.96 (s, 3H, COOCH3), 3.36 (s, CH3SO4) ppm. 13C NMR
(150 MHz, [D6]DMSO): δ = 165.5 (o, COO), 151.9 (+, C2), 148.0 (+, C4),
1-Methyl-3-(phenanthren-9-yl)quinolinium
hexafluorophosphate
(9cPF6): Methylsulfate salt 9c (0.431 g, 1.00 mmol) was dissolved in water,
then NH4PF6 (1.05 equiv) in water was added to the prepared solution.
Hexafluorophosphate salt precipitated immediately. After 0.5 h the crude
product was filtered off and washed with water (3 × 30 mL) and ethyl
acetate (3 × 30 mL), dried in vacuo to give 9cPF6. Yield 0.460 g, 99%, a
yellow solid, m.p. 223-225 °C (decomp.). 1H NMR (600 MHz, CD3CN): δ =
9.38 (d, J = 1.1 Hz, 1H), 9.23 (s, 1H), 8.90 (d, J = 8.5 Hz, 1H), 8.83 (d, J =
8.3 Hz, 1H), 8.45-8.43 (m, 1H), 8.40-8.38 (m, 1H), 8.28 (ddd, J = 1.5, 7.2,
8.9 Hz, 1H), 8.07-8.03 (m, 2H), 7.99 (s, 1H), 7.90-7.88 (m, 1H), 7.82-7.79
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10.1002/ejoc.201801648
European Journal of Organic Chemistry
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137.4 (o, C8a), 136.1 (+, C7), 134.3 (+, C5ʹ), 132.7 (+, C6ʹ), 131.8 (o, C2ʹ),
130.6 (+, C6), 130.5 (+, C4ʹ), 130.4 (+, C5), 130.2 (+, C3ʹ), 128.8 (o, C4a),
120.7 (o, C1ʹ), 119.2 (+, C8), 116.8 (o, C3), 93.4 (o, Cα), 87.4 (o, Cβ), 52.8
(+, CH3SO4), 52.5 (+, COOCH3), 45.5 (+, NCH3) ppm. IR (ATR): 2923,
2219, 1737, 1272, 1258, 1133, 1082, 832, 765, 761, 698, 556, 434 cm-1.
Spectroscopic data are in agreement with those reported in the
literature.[24]
the crude product was purified by column chromatography with petrol
ether-ethyl acetate as an eluent.
1-Methyl-3-phenylquinoline-2(1H)-thione
(11a):
According
to
Procedure 4, solution of 0.331 (1.00 mmol) of 1-methyl-3-
a
g
phenylquinolinium methylsulfate, 0.128 g (4.00 mmol) of sulfur, 0.192 g
(8.00 mmol) of LiOH, potassium tert-pentoxide (1.2 mmol, 1.7 M solution
in toluene) in 10 mL of toluene was stirred for 6 h under reflux temperature
to give 1 methyl-3-phenylquinoline-2(1H)-thione 11a. Yield 0.050 g, 20%,
1-Methyl-3-(4',5',6'-triphenyl-[1,1':2',1''-terphenyl]-3'-yl)quinolinium
methylsulfate (9g): According to Procedure 3, a solution of 0.100 g (0.171
mmol) of 2,3,4,5,6 pentaphenyl-1-(quinoline-3-yl)benzene, 50 l of
nitrobenzene and 0.06 mL (0.63 mmol) of dimethyl sulfate in 5 mL of
anhydrous toluene was heated for 2 h under reflux temperature to give 1-
methyl-3-(4',5',6'-triphenyl-[1,1':2',1''-terphenyl]-3'-yl)quinolinium
1
an orange solid, m.p. 118-119 °C. H NMR (600 MHz, CDCl3): δ = 7.67-
7.65 (m, 2H, 5-H, 7-H), 7.63-7.60 (m, 2H, 4-H, 8-H), 7.50-7.49 (m, 2H, 2ʹ-
H, 6ʹ-H), 7.44-7.41 (m, 2H, 3ʹ-H, 5ʹ-H), 7.40-7.35 (m, 2H, 6-H, 4ʹ-H), 4.41
(s, 3H, NCH3) ppm. 13C NMR (150 MHz, CDCl3): δ = 185.0 (o, C2), 143.0
(o, C3), 141.3 (o, C8a), 140.9 (o, C1ʹ), 132.1 (+, C4), 131.2 (+, C7), 129.6
(+, C2ʹ, C6ʹ), 129.1 (+, C5), 128.0 (+, C3ʹ, C5ʹ), 127.9 (+, C4ʹ), 124.3 (+,
C6), 123.8 (o, C4a), 115.8 (+, C8), 39.1 (+, NCH3) ppm. IR (ATR): 1612,
1595, 1563, 1493, 1443, 1414, 1372, 1346, 1324, 1299, 1233, 1215, 1180,
1146, 1121, 1091, 1054, 1028, 1000, 973, 964, 947, 911, 876, 852, 782,
757, 746, 740, 692, 646, 618, 595, 576, 551, 500, 481, 466, 452, 447 cm-
1. MS (ESI): m/z = 252.1 [M+H]+. HRMS (ESI): m/z calcd for C16H14NS
[M+H]+ 252.0847, found 252.0848.
methylsulfate 9g. Yield 0.122 g, 99%, a light green solid, m.p. 321-323 °C
(decomp.). 1H NMR (600 MHz, [D6]DMSO): δ = 9.35 (d, J = 1.4 Hz, 1H, 2-
H), 8.84 (s, 1H, 4-H), 8.24 (d, J = 8.1 Hz, 1H, 8-H), 8.14 (ddd, J = 1.5, 7.1,
8.8 Hz, 1H, 7-H), 8.06 (dd, J = 1.1, 8.4 Hz, 1H, 5-H), 7.92-7.90 (m, 1H, 6-
H), 7.05 (d, J = 7.7 Hz, 2H, Ph), 7.02 (d, J = 7.7 Hz, 2H, Ph), 6.96-6.82 (m,
21H, Ph), 4.34 (s, 3H, NCH3), 3.37 (s, 3H, CH3SO4) ppm. 13C NMR (150
MHz, [D6]DMSO): δ = 150.6 (+, C2), 147.5 (+, C4), 142.3 (o), 140.7 (o),
140.5 (o), 139.3 (o), 139.0 (o), 138.4 (o), 135.53 (o, C8a), 135.48 (+, C7),
134.4 (o, C3), 132.8 (o, C1ʹ), 131.0 (+), 130.7 (+), 130.64 (+), 130.60 (+),
130.54 (+), 130.5 (+, C6), 129.9 (+, C5), 127.7 (o, C4a), 127.4 (o), 126.89
(+), 126.87 (+), 126.80 (+), 126.77 (+), 126.4 (+), 125.92 (+), 125.85 (+),
118.9 (+, C8), 52.8 (+, CH3SO4), 44.8 (+, NCH3) ppm. IR (ATR): 3051,
3023, 2961, 1600, 1524, 1496, 1442, 1378, 1254, 1215, 1063, 1012, 760,
697, 618, 577, 558, 441 cm-1. HRMS (ESI): m/z calcd for C46H34N [M]+
600.2686, found 600.2687.
1-Methyl-3-(naphthalen-1-yl)quinoline-2(1H)-thione (11b): According
to Procedure 4, a solution of 0.381 g (1.00 mmol) of 1-methyl-3-
(naphthalen-1-yl)quinolinium methylsulfate, 0.128 g (4.00 mmol) of sulfur,
0.192 g (8.00 mmol) of LiOH, potassium tert-pentoxide (1.2 mmol, 1.7 M
solution in toluene) in 10 mL of toluene was stirred for 6 h under reflux
temperature to give 1 methyl-3-(naphthalen-1-yl)quinoline-2(1H)-thione
11b. Yield 0.115 g, 38%, an orange solid, m.p. 216-218 °C. 1H NMR (600
MHz, CDCl3): δ = 7.90 (d, J = 4.6 Hz, 1H, 4ʹ-H), 7.89 (d, J = 4.6 Hz, 1H, 5ʹ-
H), 7.73 (s, 1H, 4-H), 7.71-7.65 (m, 3H, 5-H, 7-H, 8-H), 7.62 (d, J = 8.4 Hz,
1H, 8ʹ-H), 7.55 (m, 1H, 3ʹ-H), 7.46 (m, 1H, 6ʹ-H), 7.42-7.36 (m, 3H, 6-H, 2ʹ-
H, 7ʹ-H), 4.45 (s, 3H, NCH3) ppm. 13C NMR (150 MHz, CDCl3): δ = 185.4
(o, C2), 142.2 (o, C3), 141.2 (o, C8a), 139.0 (o, C1ʹ), 133.7 (o, C4a), 133.4
(+, C4), 131.9 (o, C8aʹ), 131.4 (+, C7), 129.2 (+, C5), 128.6 (+, C4ʹ), 128.4
(+, C5ʹ), 126.8 (+, C2ʹ), 126.2 (+, C7), 126.0 (+, C8), 125.9 (+, C6ʹ), 125.6
(+, C3ʹ), 124.3 (+, C6), 123.7 (o, C4a), 115.9 (+, C8), 38.9 (+, NCH3) ppm.
IR (ATR): 1615, 1602, 1594, 1563, 1505, 1494, 1464, 1446, 1410, 1376,
1347, 1338, 1322, 1291, 1239, 1222, 1176, 1146, 1096, 1086, 1054, 1034,
1022, 1008, 970, 954, 943, 904, 879, 851, 796, 773, 761, 747, 731, 711,
664, 649, 637, 594, 581, 563, 511, 491, 474, 461, 452, 447, 425, 413 cm-
1. MS (ESI): m/z = 302.1 [M+H]+. HRMS (ESI): m/z calcd for C20H16NS
[M+H]+ 302.1003, found 302.1003.
1-Methyl-3-(phenanthren-9-yl)quinolin-2(1H)-one (10): Under
a
nitrogen atmosphere, 1-methyl-3-(phenanthren-9-yl)quinolinium
methylsulfate (0.431 g, 1.00 mmol), sulfur (0.128 g, 4.00 mmol) and LiOH
(0.192 g, 8.00 mmol) were suspended in absolute toluene (10 mL), and
then potassium tert butoxide (0.896 g, 8.00 mmol) was added slowly with
stirring. The resulting mixture was stirred for 6 h under reflux at 120 °C.
After that, the mixture was concentrated in vacuo, and the crude product
was purified by column chromatography with PE-EE as an eluent to give
1 methyl-3-(phenanthren-9-yl)quinolin-2(1H)-one 10. Yield 0.184 g, 55%,
a white solid, m.p. 56-57 °C (55-58 °C).[35] 1H NMR (600 MHz, CDCl3): δ =
8.77 (d, J = 8.3 Hz, 1H, 5ʹ-H), 8.72 (d, J = 8.0 Hz, 1H, 4ʹ-H), 790 (s, 1H, 4-
H), 7.88 (dd, J = 1.4, 7.8 Hz, 1H, 1ʹ-H), 7.77-7.76 (m, 2H, 5ʹ-H, 10-H), 7.68
(ddd, J = 1.4, 6.9, 8.3 Hz, 1H, 3ʹ-H), 7.66-7.64 (m, 2H, 5-H, 7-H), 7.60 (ddd,
J = 1.0, 6.9, 7.8 Hz, 1H, 2ʹ-H), 7.53 (ddd, J = 1.2, 6.9, 8.2 Hz, 1H, 7ʹ-H),
7.49 (d, J = 9.0 Hz, 1H, 8-H), 7.32-7.30 (m, 1H, 6-H), 3.86 (s, 3H, NCH3)
ppm. 13C NMR (150 MHz, CDCl3): δ = 162.0 (+, C2), 140.3 (o, C8a), 139.2
(+, C4), 134.3 (o, C9ʹ), 133.3 (o, C3), 131.7 (o, C10aʹ), 130.8 (o, C4aʹ),
130.7 (+, C7), 130.6 (o, C4bʹ), 129.1 (+, C5), 128.9 (+,C1ʹ), 128.4 (+, C10ʹ),
127.0 (+, C3ʹ), 126.79 (+, C8ʹ), 126.77 (+, C2ʹ), 126.73 (+, C7ʹ), 126.68 (+,
C6ʹ), 123.1 (+, C5ʹ), 122.7 (+, C4ʹ), 122.5 (+, C6), 120.8 (o, C4a), 114.4 (+,
C8), 30.2 (+, NCH3) ppm. IR (ATR): 3059, 1638, 1590, 1570, 1528, 1495,
1463, 1448, 1432, 1416, 1383, 1364, 1343, 1329, 1317, 1295, 1275, 1242,
1211, 1164, 1146, 1127, 1105, 1085, 1040, 1018, 1001, 979, 951, 927,
918, 899, 884, 861, 853, 805, 788, 769, 753, 748, 732, 721, 710, 660, 620,
615, 578, 558, 543, 509, 496, 482, 463, 454, 426, 416, 412, 407 cm-1. MS
(ESI): m/z = 336.0 [M+H]+.
1-Methyl-3-(phenanthren-9-yl)quinoline-2(1H)-thione (11c): According
to Procedure 4, a solution of 0.431 g (1.00 mmol) of 1-methyl-3-
(phenanthren-9-yl)quinolinium methylsulfate, 0.128 g (4.00 mmol) of sulfur,
0.192 g (8.00 mmol) of LiOH, potassium tert-pentoxide (1.2 mmol, 1.7 M
solution in toluene) in 10 mL of toluene was stirred for 6 h under reflux
temperature to give 1 methyl-3-(phenanthren-9-yl)quinoline-2(1H)-thione
11c. Yield 0.316 g, 90%, an orange solid, m.p. 227-228 °C. 1H NMR (600
MHz, CDCl3): δ = 8.75 (d, J = 8.3 Hz, 1H, 5ʹ-H), 8.73 (d, J = 8.3 Hz, 1H, 4ʹ-
H), 7.88 (d, J = 7.9 Hz, 1H, 1ʹ-H), 7.81 (s, 1H, 4-H), 7.74-7.66 (m, 6H, 4-H,
7-H, 8-H, 3ʹ-H, 8ʹ-H, 10ʹ-H), 7.63 (ddd, J = 1.2, 7.1, 8.2 Hz, 1H, 6ʹ-H), 7.60
(ddd, J = 0.8, 7.1, 7.7 Hz, 1H, 2ʹ-H), 7.49 (ddd, J = 1.1, 7.0, 8.1 Hz, 1H, 7ʹ-
H), 7.40 (ddd, J = 1.2, 7.0, 8.0 Hz, 1H, 6-H), 4.47 (s, 3H, NCH3) ppm. 13
C
NMR (150 MHz, CDCl3): δ = 185.3 (o, C2), 142.5 (o, C3), 141.2 (o, C8a),
137.9 (o, C9ʹ), 133.6 (+, C4), 131.9 (o, C10a), 131.4 (+, C7), 131.1 (o,
C8aʹ), 130.6 (o, C4aʹ), 130.5 (o, C4bʹ), 129.2 (+, C5), 128.9 (+, C1ʹ), 127.3
(+, C10ʹ), 127.0 (+, C8ʹ), 126.9 (+, C3ʹ), 126.8 (+, C2ʹ), 126.6 (+, C7ʹ), 126.6
(+, C6ʹ), 124.3 (+, C6), 123.7 (o, C4a), 123.1 (+, C5), 122.8 (+, C4ʹ), 115.9
(+, C8), 38.8 (+, NCH3) ppm. IR (ATR): 1611, 1595, 1563, 1525, 1494,
1456, 1449, 1424, 1386, 1369, 1347, 1328, 1309, 1271, 1244, 1233, 1210,
1185, 1166, 1144, 1110, 1097, 1088, 1038, 1009, 951, 945, 915, 909, 892,
General procedure for the preparation of thiones (Procedure 4):
Under a nitrogen atmosphere the corresponding salt (1.00 mmol), sulfur
(4.00 mmol) and LiOH (8.00 mmol) were suspended in absolute toluene
(10 mL), and then potassium tert-pentoxide (1.20 mmol, 1.7 M solution in
toluene) was added slowly with stirring. The resulting mixture was stirred
for 6 h under reflux at 120 °C. After the mixture was concentrated in vacuo,
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10.1002/ejoc.201801648
European Journal of Organic Chemistry
FULL PAPER
874, 857, 846, 783, 759, 749, 739, 721, 701, 658, 636, 617, 611, 582, 557,
529, 506, 499, 486, 428 cm-1. MS (ESI): m/z = 352.1 [M+H]+. HRMS (ESI):
m/z calcd for C24H18NS [M+H]+ 352.1160, found 352.1155.
C4), 131.7 (+, C7), 129.4 (+, C5), 128.5 (+, C5 ʹ), 128.3 (+, C4 ʹ), 127.0 (+,
C2ʹ), 126.1 (+, C7ʹ), 126.0 (+, C8ʹ), 125.9 (+, C6), 125.6 (+, C3ʹ), 125.0 (+,
C6ʹ), 124.9 (o, C4a), 116.4 (+, C8), 43.7 (+, NCH3) ppm. 77Se NMR (114
MHz, CDCl3) δ = 716.8 ppm. IR (ATR): 3051, 3017, 2919, 2849, 2185,
1967, 1733, 1610, 1560, 1373, 1238, 1145, 1096, 1067, 795, 773, 761,
581, 491, 423 cm-1. HRMS (APCI): m/z calcd for C20H16NSe [M+H]+
350.0443, found 350.0441.
1-Methyl-3-(4',5',6'-triphenyl-[1,1':2',1''-terphenyl]-3'-yl)quinoline-
2(1H)-thione (11g): According to Procedure 4, a solution of 0.154 g (0.22
mmol)
of
2,3,4,5,6-phenyl-1-(1-methylquinolinium-3-yl)benzene
methylsulfate, 0.055 g (1.72 mmol) of sulfur, 0.042 g (1.82 mmol) of LiOH,
potassium tert-pentoxide (0.26 mmol, 1.7 M solution in toluene) in 5 mL of
toluene was stirred for 6 h under reflux temperature to give thione 11g.
Yield 0.050 g, 38%, a yellow solid, m.p. ˃330 °C. 1H NMR (600 MHz,
CDCl3): δ = 7.46 (ddd, J = 1.6, 7.1, 8.7 Hz, 1H, 7-H), 7.41 (s, 1H, 4-H),
7.39 (dd, J = 1.5, 7.8 Hz, 1H, 5-H), 7.37-7.36 (m, 2H, Ph), 7.30 (d, J = 8.6
Hz, 1H, 8-H), 7.17 (ddd, J = 0.7, 7.2, 8.1 Hz, 1H, 6-H), 6.93-6.76 (m, 23H,
Ph), 4.00 (s, 3H, NCH3) ppm. 13C NMR (150 MHz, CDCl3): δ = 184.7 (o,
C2), 142.4 (o, C3), 140.8 (o), 140.65 (o), 140.61 (o), 140.5 (o), 140.03 (o),
139.99 (o, C8a), 138.8 (o), 135.3 (+, C4), 131.9 (+), 131.8 (+), 131.6 (+),
131.4 (+), 131.1 (+), 130.9 (+), 130.5 (+, C7), 128.6 (+, C5), 126.80 (+),
126.76 (+), 126.54 (+), 126.47 (+), 126.0 (+), 125.7 (+), 125.2 (+), 123.5
(+, C6), 122.9 (o, C4a), 115.4 (+, C8), 38.4 (+, NCH3) ppm. IR (ATR): 3055,
3022, 2922, 2850, 1733, 1616, 1568, 1495, 1441, 1372, 1315, 1235, 1184,
1148, 1095, 1072, 1043, 1027, 909, 792, 740, 695, 644, 552, 502, 481 cm-
1. HRMS (ESI): m/z calcd for C46H33NNaS [M+Na]+ 654.2220, found
654.2200.
1-Methyl-3-(phenanthren-9-yl)quinoline-2(1H)-selenone
(12c):
According to Procedure 5, a solution of 0.431 g (1.00 mmol) of 1-methyl-
3-(phenanthren-9-yl)quinolinium methylsulfate, 0.316 g (4.00 mmol) of
selenium, 0.192 g (8.00 mmol) of LiOH, potassium tert-pentoxide (1.2
mmol, 1.7 M solution in toluene) in 10 mL of toluene was stirred for 6 h
under reflux temperature to give 1 methyl-3-(phenanthren-9-yl)quinoline-
2(1H)-selenone 12c. Yield 0.080 g, 20%, a red solid, m.p. 271-272 °C. 1H
NMR (600 MHz, CDCl3): δ = 8.75 (d, J = 8.3 Hz, 1H, 5ʹ-H), 8.73 (d, J = 8.0
Hz, 1H, 4ʹ-H), 7.90 (s, 1H, 4-H), 7.87 (d, J = 7.8 Hz, 1H, 1ʹ-H), 7.83 (d, J =
8.6 Hz, 1H, 8-H), 7.77 (ddd, J = 1.6, 7.1, 8.8 Hz, 1H, 7-H), 7.72 (dd, J =
1.5, 7.8 Hz, 1H, 5-H), 7.69-7.65 (m, 3H, 3ʹ-H, 8ʹ-H, 10ʹ-H), 7.63 (ddd, J =
1.3, 6.9, 8.3 Hz, 1H, 6ʹ-H), 7.60 (ddd, J = 1.0, 7.0, 7.9 Hz, 1H, 2ʹ-H), 7.49-
7.45 (m, 2H, 6-H, 7ʹ-H), 4.61 (s, 3H, NCH3) ppm. 13C NMR (150 MHz,
CDCl3(deptq)): δ = 186.8 (-, C2), 146.2 (-, C3), 141.9 (-, C8a), 139.0 (-,
C9ʹ), 132.1 (+, C4), 131.9 (-, C10aʹ), 131.7 (+, C7), 131.3 (-, C8aʹ), 130.5
(-, C4aʹ), 130.5 (-, C4bʹ), 129.5 (+, C5), 129.0 (+, C1ʹ), 127.5 (+, C9ʹ), 127.1
(+, C8ʹ), 126.9 (+, C3ʹ), 126.8 (+, C2ʹ), 126.6 (+, C6ʹ, C7ʹ), 125.1 (+, C6),
125.0 (-, C4a), 123.1 (+, C5ʹ), 122.9 (+, C4ʹ), 116.5 (+, C8), 43.6 (+, NCH3)
ppm. 77Se NMR (114 MHz, CDCl3) δ = 720.4 ppm. IR (ATR): 1591, 1561,
1449, 1367, 1211, 1135, 1065, 908, 890, 759, 749, 740, 721, 611, 556,
488, 428 cm-1. HRMS (ESI): m/z calcd for C24H17NNaSe [M+Na]+ 422.0413,
found 422.0411.
General procedure for the preparation of selenones (Procedure 5):
Under a nitrogen atmosphere, the corresponding salt (1.00 mmol),
selenium (4.00 mmol) and LiOH (8.00 mmol) were suspended in absolute
toluene (10 mL), then potassium tert-pentoxide (1.20 mmol, 1.7 M solution
in toluene) was added slowly with stirring. The resulting mixture was stirred
for 6 h under reflux at 120 °C. Afterward, the mixture was concentrated in
vacuo and the crude product was purified by column chromatography with
petrol ether-ethyl acetate as eluent.
1-Methyl-3-(phenanthren-9-yl)-N,N-bis(trimethylsilyl)-1,2-
dihydroquinolin-2-amine
(13):
1-Methyl-3-(phenanthren-9-
yl)quinolinium hexafluorophosphate (0.015 g, 0.032 mmol) and 2 M
solution of LiHMDS in THF (0.02 mL, 0.380 mmol) were used for the NMR
experiment. 1H NMR (600 MHz, [D8]THF): δ = 8.76 (d, J = 8.3 Hz, 1H, 5ʹ-
H), 8.71 (d, J = 8.1 Hz, 1H, 4ʹ-H), 8.18 (d, J = 8.1 Hz, 1H, 1ʹ-H), 7.89 (s,
1H, 10ʹ-H), 7.85 (d, J = 7.9 Hz, 1H, 8ʹ-H), 7.60-7.56 (m, 2H, 3ʹ-H, 6ʹ-H),
7.53-7.49 (m, 2H, 2ʹ-H, 7ʹ-H), 7.17 (t, J = 7.8 Hz, 1H, 7-H), 7.13 (d, J = 7.1
Hz, 1H, 5-H), 6.81 (d, J = 8.1 Hz, 1H, 8-H), 6.76 (s, 1H, 4-H), 6.71 (t, J =
7.3 Hz, 1H, 6-H), 5.58 (s, 1H, 2-H), 3.19 (s, 3H, NCH3), 0.00 (s, 18H,
NSi2(CH3)6) ppm. 13C NMR (150 MHz, [D8]THF): δ = 141.5 (o, C8a), 136.9
(o, C9ʹ), 133.1 (o, C3), 131.8 (o, C10aʹ), 131.0 (o, C8aʹ), 130.8 (o, C4aʹ),
130.0 (o, C4bʹ), 128.6 (+, C7), 128.4 (+, C8ʹ), 127.4 (+, C10ʹ), 126.51 (+,
C1ʹ), 126.46 (+, C7ʹ), 126.42 (+, C4), 126.3 (+, C6ʹ), 126.2 (+, C2ʹ), 126.1
(+, C3ʹ), 122.9 (+, C5), 122.4 (+, C4ʹ), 121.1 (o, C4a), 116.9 (+, C6), 111.2
(+, C8), 83.6 (+, C2), 35.4 (+, NCH3), 1.7 (+, NSi2(CH3)6) ppm.
1-Methyl-3-phenylquinoline-2(1H)-selenone (12a): According to
Procedure 5,
a solution of 0.331 g (1.00 mmol) of 1-methyl-3-
phenylquinolinium methylsulfate, 0.316 g (4.00 mmol) of selenium, 0.192
g (8.00 mmol) of LiOH, potassium tert-pentoxide (1.2 mmol, 1.7 M solution
in toluene) in 10 mL of toluene was stirred for 6 h under reflux temperature
to give 1 methyl-3-phenylquinoline-2(1H)-selenone 12a. Yield 0.059 g,
20%, a red oil. 1H NMR (600 MHz, CDCl3): δ = 7.74–7.69 (m, 4H, 4-H, 5-
H, 7-H, 8-H), 7.47–7.37 (m, 6H, 6-H, 2ʹ-H, 3ʹ-H, 4ʹ-H, 5ʹ-H, 6ʹ-H), 4.56 (s,
3H, NCH3) ppm. 13C NMR (150 MHz, CDCl3): δ = 186.4 (o, C2), 146.7 (o,
C3), 142.7 (o, C1ʹ), 141.5 (o, C8a), 131.4 (+, C7), 130.4 (+, C4), 129.7 (+,
C2ʹ, C6ʹ), 129.3 (+, C5), 127.9 (+, C3ʹ, C4ʹ, C5ʹ), 125.0 (+, C6), 125.0 (o,
C4a), 116.4 (+, C8), 43.9 (+, NCH3) ppm. 77Se NMR (114 MHz, CDCl3) δ
= 706.6 ppm. IR (ATR): 1639, 1591, 1559, 1493, 1443, 1371, 1321, 1234,
1142, 1070, 907, 790, 743, 694, 638, 590, 576, 480 cm-1. HRMS (APCI):
m/z calcd for C16H14NSe [M+H]+ 300.0286, found 300.0275.
Acknowledgments
1-Methyl-3-(naphthalen-1-yl)quinoline-2(1H)-selenone
(12b):
According to Procedure 5, a solution of 0.381 g (1.00 mmol) of 1-methyl-
3-(naphthalen-1-yl)quinolinium methylsulfate, 0.316 g (4.00 mmol) of
selenium, 0.192 g (8.00 mmol) of LiOH, potassium tert-pentoxide (1.2
mmol, 1.7 M solution in toluene) in 10 mL of toluene was stirred for 6 h
under reflux temperature to give 1 methyl-3-(naphthalen-1-yl)quinoline-
2(1H)-selenone 12b. Yield 0.220 g, 63%, a red solid, m.p. 196-198 °C
(decomp.). 1H NMR (600 MHz, CDCl3): 7.90 (m, 2H, 4ʹ-H, 5ʹ-H), 7.82 (s,
1H, 4-H), 7.80 (d, J = 8.7 Hz, 1H, 8-H), 7.75 (ddd, J = 1.5, 7.1, 8.7 Hz, 1H,
7-H), 7.70 (dd, J = 1.5, 7.8 Hz, 1H, 5-H) 7.61 (d, J = 8.4 Hz, 1H, 8ʹ-H), 7.56
(dd, J = 6.9, 8.2 Hz, 1H, 3ʹ-H), 7.47-4.43 (m, 2H, 6-H, 6ʹ-H) 7.42 (dd, J =
1.1, 7.0 Hz, 1H, 2ʹ-H), 7.38 (ddd, J = 1.4, 6.9, 8.4 Hz, 1H, 7ʹ-H), 4.59 (s,
3H, NCH3) ppm. 13C NMR (150 MHz, CDCl3): δ = 186.8 (o, C2), 145.9 (o,
C3),141.8 (o, 8a), 140.3 (o, C1ʹ), 133.6 (o, C4aʹ), 132.0 (o, C8aʹ), 131.8 (+,
Dr. Gerald Dräger, university of Hannover (Germany) is gratefully
acknowledged for measuring a part of the HRMS spectra.
Keywords: quinoline • carbene • selenones • heterocycle
synthesis • quinolin-2-ylidene
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Entry for the Table of Contents
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Series of substituted quinolinium salts
were prepared which possess aryl
groups or ethynyl groups in position 3.
For R = aryl N-heterocyclic carbene
trapping reactions were performed
with sulfur and selenium in the
N-Heterocyclic Carbenes
Sviatoslav Batsyts, Roman Vedmid, Jan
C. Namyslo, Martin Nieger, and Andreas
Schmidt*
Page No. – Page No.
presence of potassium tert-pentoxide
and lithium hydroxide.
3-Aryl Substituted 1-
Methylquinolinium Salts as Carbene
Precursors
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