Synthesis and characterization of propeller-shaped mono- to hexacationic quinolinium-substituted benzenes

Article abstract of DOI:10.1039/c9ob00357f

Diels-Alder reaction of 2-, 3- and 4-(phenylethynyl)quinolines and tetraphenylcyclopentadienone gave three regioisomeric 2,3,4,5,6-pentaphenyl-1-(quinolin-2-yl, -3-yl, and -4-yl)benzenes. Restricted rotation of the 3-yl and 4-yl substituted derivatives is observed between the central core and the substituents, resulting in propeller-shaped molecules. Likewise, 1,2-diquinolinyl-3,4,5,6-tetraphenylbenzenes with 3-yl,3-yl and 3-yl,4-yl connectivity were prepared. As evidenced by NMR spectroscopy, they form two diasteromers due to their restricted rotation. A cobalt-catalyzed [2 + 2 + 2]-cyclotrimerization of 2-(phenylethynyl)quinoline resulted in the formation of triphenyl-2,4,6- and -3,5,6-tri(quinolin-2-yl)benzenes. The same reaction was applied to 3,3′-ethyne-1,2-diyldiquinoline which formed hexa(quinolin-3-yl)benzene. N-Methylation gave the title compounds. Among those, the hexacationic hexa(N-methylquinolinio-3-yl)benzene is described. Stereochemical aspects are predominantly discussed by means of results of NMR experiments. DFT-calculations on the most stable conformations and the frontier orbital profiles of the hexacation as well as of its neutral precursor have been carried out.

Full text of DOI:10.1039/c9ob00357f

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DOI: 10.1039/C9OB00357F
Journal Name
ARTICLE
Synthesis and characterization of propeller-shaped mono- to
hexacationic quinolinium-substituted benzenes
a
a
a
b
a
Sviatoslav Batsyts, Eike G. Hübner, Jan C. Namyslo, Mimoza Gjikaj, and Andreas Schmidt *
Received 00th January 2019,
Accepted 00th January 2019
Diels-Alder reaction of 2-, 3- and 4-(phenylethynyl)quinolines and tetraphenylcyclopentadienone gave three regioisomeric
DOI: 10.1039/x0xx00000x
2
,3,4,5,6-pentaphenyl-1-(quinolin-2-yl, -3-yl, and -4-yl)benzenes. Restricted rotation of the 3-yl and 4-yl substituted
derivatives is observed between the central core and the substituents, resulting in propeller-shaped molecules. Likewise,
,2-diquinolinyl-3,4,5,6-tetraphenylbenzenes with 3-yl,3-yl and 3-yl,4-yl connectivity were prepared. As evidenced by NMR
spectroscopy, they form two diasteromers due to their restricted rotation. A cobalt-catalyzed [2+2+2]-cyclotrimerization of
-(phenylethynyl)quinoline resulted in the formation of triphenyl-2,4,6- and -3,5,6-tri(quinolin-2-yl)benzenes. The same
www.rsc.org/
1
2
reaction was applied to 3,3'-ethyne-1,2-diyldiquinoline which formed hexa(quinolin-3-yl)benzene. N-Methylation gave the
title compounds. Among those, the hexacationic hexa(N-methylquinolinio-3-yl)benzene is described. Stereochemical
aspects are predominantly discussed by means of results of NMR experiments. DFT-calculations on the most stable
conformations and the frontier orbital profiles of the hexacation as well as of its neutral precursor have been carried out.
potential semiconductors,15 photosensitive materials,
16
1
7
18
Introduction
Considerable attention has been directed toward heterocycle
polycations as they are interesting in natural product chemistry,
heterocyclic chemistry, and materials chemistry. Thus,
oxidants, and biologically active compounds like herbicides,
1
9
acetylcholinesterase reactivators,
and cholinesterase
inhibitors. A recent review article summarizes results
2
0
2
1
achieved so far.
1
2
polypyridinium alkaloids (halitoxin, cyclostellettamin C,
NMe2
N
4
Cl
Me
O
5 OTf
NMe2
3
4
5
6
amphitoxin, viscosamine, viscosaline, pachychalines A-C ) are
polycationic molecules from nature. Streitwieser et al. reported
on series of polypyridinium salts and betaines which have
Me2N
O
N
N
N
Me2N
N
NMe2
N
7
N
adjacent heteroarenium rings in conjugation. Thus, the five-
fold pyridinium substituted cyclopentadiene anion 1 possesses
N
8
N
N
2
Me N
NMe2
structure elements of conjugated mesomeric betaines. The
SASAPOS protocol (self-activated silyl-assisted polyonio
substitution) by Weiss et al. allowed for the synthesis of a
variety of heteroarenium substituted substrates, for which 2 is
Me2N
NMe2
NMe2
2
1
5
OTf
N
N
9
10
given as an example here. This widely applicable protocol
Me Me
N
N
N
N
N
N
N
takes advantage of the fact that a substrate which bonds neutral
ligands such as chloride undergoes a substitution with
heteroaromatic nucleophiles equivalent to the quantity of the
bonding ligands in the presence of the same number of
equivalents of trimethylsilyltriflate (TMSOTf). We reported on
heterocycle polycations with heteroaromatic central cores such
N
N
3
N
N
N
Me
N
N
N
4
1
1
12
13
13
as pyridine, pyrimidine, pyrazine, pyridazine, 1,3,5-
1
3
13
14
triazine, and purine. An example is pentacation 3. Pyridine
polycations proved to be versatile starting materials for the
synthesis of highly substituted pyridines with various
1
1
substitution patterns.
Apart from their synthetic
applicabilities, heterocycle polycations are of interest as
5
a
Clausthal University of Technology, Institute of Organic Chemistry, Leibnizstraße
, D-38678 Clausthal-Zellerfeld, Germany. Email: schmidt@ioc.tu-clausthal.de
Clausthal University of Technology, Institute of Inorganic and Analytical
Chemistry, Paul-Ernst-Straße 4, D-38678 Clausthal-Zellerfeld, Germany.
Scheme 1. Examples of heterocycle polycations and of
propeller-shaped molecules
6
b
Electronic Supplementary Information (ESI) available: Calculations, NMR spectra.
See DOI: 10.1039/x0xx00000x
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Steric hindrance exerted by the peripheral ligands cause known that methyl and methoxy groups in C
Journal Name
Ar systems in
6
View Article Online
6
propeller-shaped molecules. Recently, the sterically congested ortho position cause a barrier of rotationDOoIf: 1a0p.1p0r3o9/xCim9OaBt0e0ly35373F
hexa(heteroaryl)benzene (HHAB) 4 was formed as two isolable kcal/mol, whereas this value is considerably decreased to
2
3
isomers which differ only in the rotation of one methyl-pyridine approximately 17 kcal/mol for the case of meta-substitutions.
2
2
group. In general, propeller-shaped hexaarylbenzenes (HABs) Hexaphenylbenzene C
6
Ph
6
consequently displays one set of
have numerous signals in the C NMR spectra and one overlapped signal with a
2
3
13
such as hexa(-naphthyl)benzene
5
applications in materials sciences as they play roles as liquid center of gravity at 6.83 ppm (30H) in the proton resonance
crystals,24 microporous organic solids, molecular capsules,
25
26
spectra. The chemical shifts of 10a-c are different as a
35
2
7
28
supramolecular electronic materials, molecular rotors,
consequence of their isomerism and, in addition,
2
9
30
nonlinear optical materials,
metal sensors,
redox intermolecular interactions (Fig. 1). The broadening of the
materials,31 and molecular wires. We report here on signals at approximately 7.00 ppm in the spectrum of 10a (blue)
32
…
quinolinium-substituted benzenes which combine the features can be attributed to N H-C interactions to the nitrogen atom,
of HHABs and polycations as they have to adopt propeller- which is not possible in 10b,c. These interactions are thought to
shaped configurations due to the additional benzo-annulation be within the limits of hydrogen bonds and classical van der
3
6
in comparison to their pyridinium derivatives.
Waals contacts. The upfield shift of phenyl ring signals due to
intramolecular -interactions caused by the quinolin-4-yl
substitution of 10c can clearly be seen (black), which are less in
Results and discussion
1
0a,b.
First, Sonogashira-Hagihara coupling reactions were used to
prepare three isomeric ethynyl-substituted quinolines as
starting materials for the synthesis of monoquinolinyl-
substituted pentaphenylbenzenes, which are of potential
interest as ligands of organic electroluminescent device
materials.33 Thus, the 2-, 3-, and 4-halosubstituted quinolines
N
N
6
8
a-c and phenylacetylene 7 were reacted to give the quinolines
a-c in good yields (Scheme 2). With these compounds in hand,
N
we examined the [4+2]-cycloaddition with tetraphenylcyclo-
pentadione 9. The reaction did not proceed under a variety of
different conditions that were tested, among those reflux
temperature in benzene, toluene, and xylene, respectively. On
increasing the reaction temperature to 305 °C by using
benzophenone as a solvent, however, the quinolines 10a-c
were finally prepared within 30 min. in moderate yields.
H
H
N
N
N
H
H
10a
10b
10c
X
Pd(PPh3)2Cl2, CuI,
NEt3 (abs), N2, 1.5-2 h,
reflux
+
N
1
Figure 1. Comparison of H NMR spectra of HHABs 10a (1), 10b (2),
and 10c (3) (DMSO-d , 25 °C).
N
6
6a: X = 2-Cl
6b: X = 3-Br
6c: X = 4-Br
7
8a: 2-yl (95%)
8b: 3-yl (100%)
8c: 4-yl (98%)
The steric hindrance of the quinoline rings can be compared
3
7
Ph
Ph
Ph
Ph
with 1-(3,4-dimethylphenyl)-2,3,4,5,6-pentaphenylbenzene
Ph
Ph
Ph
O
for 10a,b and 1-(2,3-dimethylphenyl)-2,3,4,5,6-pentaphenyl-
benzene, which seems to be unknown, for 10c. However, the
quinolin-4-yl-substitution pattern of 10c imitates the steric
hindrance of the methyl group in the model compound 1-(2-
(9)
C
Ph
Ph
Ph
Ph -CO
Ph
O
N
Ph
0.85-1.5 eq. of 9,
benzophenone,
Q Ph
1
1
1
0a: 2-yl (64%)
0b: 3-yl (51%)
0c: 4-yl (81%)
30 min., reflux
methylphenyl)-2,3,4,5,6-pentaphenylbenzene which has
a
3
8
propeller-type topology in the solid and a slow rotation of the
3
9
o-tolyl group 25 °C in solution. For the case of free rotation
Scheme 2. Synthesis of monoquinoline-substituted HHABs.
1
3
under the measurement conditions, 25 distinct C NMR
resonance frequencies can be expected for 10a-c, among those
Similar to hexaphenylbenzene, the six peripheral rings of 10a-c
cannot lie in the plane of the central benzene ring. Whereas in
solution, on the NMR time scale, the peripheral rings are
perpendicular to the plane of the central ring in the absence of
appropriate substitutions, the X-ray structure of
hexaphenylbenzene itself showed a propeller conformation
1
5 signals of CH groups. For the case of restricted rotation, this
1
3
number is increased to 29 C NMR signals in total, and 19
signals of CH groups, because the ortho- and meta-positions of
the 2- and 3-phenyl substituents become non-isochronous. The
least sterically hindered compound 10a displays 22 distinct
6
signals due to overlapping in DMSO-d at 25 °C. Compound 10b
3
4
with angles around the Ph-Ph bonds of approximately 65°. It is
2
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shows the expected 29 signals for a restricted rotation, and 10c
displays in total 27 distinct resonance frequencies under the
same measurement conditions, presumably due to overlapping
of two signals.
OH
View Article Online
DOI: 10.1039/C9OB00357F
MEBYNOL,
Pd(PPh3)2Cl2, CuI,
NEt3 (abs), N2,
6b/6c,
KOH/K3PO4,
toluene (abs.),
reflux
Pd(PPh3)2Cl2, CuI,
NEt3 (abs), N2,
2.5-3 h, reflux
N
1.5h, reflux
6b
N
N
The same protocol was applied to the reaction of quinoline 14
with two alkynyl residues which was prepared in 21% yield in
three steps from 1,4-dibromobenzene 11 via 12 and 13 as
shown (Scheme 3). Quinoline 14 reacted with an excess of
cyclopentadienone 9 to give compound 15 which precipitated
as exclusive reaction product during the work-up procedure in
good yield.
N
16 (99%)
17 (95%)
1
1
8a: 3-yl (70%)
8b: 4-yl (56%)
1.5 eq. of 9,
benzophenone,
reflux
N
3
N
3
4
18a/18b
+
4
N
3
OH
N
MEBYNOL,
0.95 eq. of 6b
Pd(PPh3)2Cl2, CuI,
NEt3 (abs), N2, 3 h,
reflux
KOH, K3PO4,
toluene (abs),
15 min., reflux
Pd(PPh ) Cl , CuI,
Br
Br
3
2
2
19a: 3-yl,3-yl (90%)
19b: 3-yl,4-yl (78%)
NEt3 (abs), N , 3 h,
2
reflux
Scheme 4. Synthesis of diquinoline-substituted HHABs.
N
For the synthesis of HHABs with three quinoline residues
another approach was applied. Thus, the asymmetric acetylene
HO
11
12 (99%)
13 (62%)
14 (35%)
8
a was subjected to a cobalt-catalyzed [2+2+2]-trimerization
reaction which has already been applied for the synthesis of
HABs before (Scheme 5). The trimerization of 8a gave a
3
eq. of 9,
benzophenone,
reflux, 30 min.
41
mixture of two separable regioisomers 20a and 20b (1:3) with a
total yield of 40%. Compound 20a is a heteroaromatic analogue
of 1,3,5-tri(-naphthyl)-benzene, a propeller-like, non-planar
N
4
2
molecule that is known to interlock in the melt. It displays 15
1
3
15 (77%)
C NMR signals, similar to the corresponding number of signals
of D3h symmetric oligophenylenes which were expected within
4
3
the fast exchange limit for all single bond rotations. Similar to
the spectra of the mono(quinolin-2-yl)derivative 10a, the
signals of the ortho- and meta-protons appear as broad singlets
Scheme 3. Synthesis of a bulky monoquinoline HHAB.
The method is also applicable to prepare isomeric diquinolinyl
substituted tetraphenylbenzenes (Scheme 4). Thus, under
analogous conditions, the compound 19a with quinolin-3-yl/3-
yl connectivity and the isomeric quinolin-3-yl/4-yl derivative
…
due to N H-C interactions. Assignment of all atoms using 2D
spectra was possible; one set of proton signals for all three
quinoline residues of 20a was found. It is known that ortho-
substitutions, which cannot be taken as a model for the
quinolin-2-yl substitution, can prevent rapid interconversion of
1
9b were prepared in 90% and 78% yield, respectively, starting
from 18a,b which are available starting from 6b,c and 17 by
standard procedures. The quinolin-3-yl,3-yl compound 19a can
exist in two diastereomeric forms due to restricted rotation, a
the C3v and C
formation of syn- and anti-conformations.
s
isomeric forms which are the result of the
44
The 1,2,4-
substituted compound 20b displays 36 of expectable 45 distinct
C
s
conformation and a racemic pair with C
2
symmetry, similar to 13
C NMR resonance frequencies in DMSO-d
6
at 25 °C, if free
hexaarylbenzenes with two meta-substituents at 0°C on the
rotation under the measurement conditions is presumed.
3
4,40
1
NMR time scale.
The H NMR spectrum of 19a showed 37 of
expectable 48 C NMR signals. Two sets of partially overlapped
signals can be identified in a ratio of 1:0.8 under the measuring
1
Similar to compound 10a, a considerable broadening of the H
1
3
NMR signals of the quinolines in DMSO-d
phenyl rings is observable.
6
at 25 °C as well as the
conditions (DMSO-d
6
, 25 °C). The 4-H hydrogen atom of the
quinoline residues of one isomer appears at 7.97 ppm, whereas
Co2(CO)8,
dioxane (abs.),
reflux, 14 h
N
1
3
the other is detectable at 7.93 ppm. The C NMR spectrum of
isomer 19b, which possesses a quinolin-3-yl,4-yl connectivity,
shows 72 distinct signals of expectable 96. This number is due
to the fact, that the 3-yl,4-yl connectivity causes an additional
non-symmetry of the molecule and consequently non-
isochronous substituents of the two magnetically inequivalent
isomers. Under the same measuring conditions, two
isochronous rotameric forms are present in a ratio of 1:1 in the
NMR spectrum of 19b.
N
N
N
N
+
N
N
8a
20a (10%)
20b (30%)
Scheme 5. Cobalt-catalyzed [2+2+2]-cyclotrimerization.
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Trimerization of the acetylene 18a was tested to prepare a
hexaquinolin-3-yl substituted benzene. Indeed, HHAB 21 was
formed in 85% yield (Scheme 6). Unfortunately, due to the
rather limited solubility of 21 NMR analyses were not possible.
Nonetheless, the corresponding HRMS (m/z = 863.2896) is in
accord with the structure of 21 which can exist in eight
rotameric forms. Literature-known calculated minimized
energies of hexa(-naphthyl)benzene, the non-heteroaromatic
analogue of 21, revealed that the most stable rotamer is the one
in which all -naphthyl residues are twisted onto the same side
View Article Online
DOI: 10.1039/C9OB00357F
Ph
Ph
Ph
Ph
Me2SO4,
toluene (abs.),
Ph reflux
Ph
Ph
Ph
Ph
22a: 2-yl (95%)
22b: 3-yl (99%)
22c: 4-yl (99%)
Ph
N
N
2
3
MeSO4
Me
1
0a-c
Ph
Ph
Ph
Ph
Ph
Ph
Ph
(6,0). The X-ray crystal analysis of hexa(2-pyridyl)benzene,
Ph Me2SO4,
toluene (abs.),
reflux
NH4PF6,
water
however, revealed the α,β,α,β,α,β arrangement of pyridine
N
N
23PF6 (95%)
rings and dihedral angles between the pyridyl substituent and
Me
2
2
the benzene ring of approximately 90°.
Ph
Ph
Ph
Ph
MeSO4
Ph
3 (96%) Ph
Ph
Ph
2
15
N
N
Ph
Ph
Ph
Ph
1
. Me2SO4,
toluene (abs.),
reflux
Co2(CO)8,
dioxane (abs.),
reflux, 14 h
N
Ph
Ph
Ph
Ph
N
2. NH4PF6,
water
N
N
N
N
N
N
Me 2PF6
N
19a: 3-yl
19b: 4-yl
Me
N
2
2
4a: 3-yl (95%)
4b: 4-yl (90%)
18a
21 (85%)
Scheme 7. Methylation of quinoline-based HHABs.
Scheme 6. Cobalt-catalyzed [2+2+2]-cyclotrimerization of 18a.
Finally, N-methylation of 21 with an excess of dimethyl sulfate
followed by precipitation with NH
methylated hexacationic HHAB 25 (Scheme 8) which is soluble
4 6
PF successfully gave the fully
Synthesis of polycationic HABs
Based on former experiences of our group,45 dimethyl sulfate
in DMSO-d and which could be characterized completely.
6
was used as a methylation agent to convert the quinoline
derivatives into cationic species. First, the monoquinoline
substituted HABs 10a-c were successfully methylated in
anhydrous toluene under reflux conditions (Scheme 7). The N-
Me
N
N
Me
1
. Me2SO4,
toluene (abs.),
reflux
N
N
N
NMe
1
3
methyl group of 22a interlocks the molecule and 19 distinct
C
2. NH4PF6,
water
NMR signals of CH groups are detectable plus the signals of the
anion and the methyl group at 52.8 and 42.5 ppm, respectively.
Thus, in contrast to 10a-c, 22a-c all display the same number of
signals. The N-methylquinolinium salts of 15 with methylsulfate
Me
N
N
N
N
Me
N
N
Me
6
(23) and hexafluorophosphate anions (23PF ) were prepared as
21
25
well, and the diquinoline HABs 19a,b were also successfully
methylated. An immediate anion exchange reaction during
work-up yielded the dihexafluorophosphate salts 24a,b. Similar
to the non-methylated precursors 19a and 19b, the number of
C NMR resonance frequencies of 24a and 24b is 38 and 72,
respectively. The 3-yl,3-yl salt 24a has an almost identical ratio
Scheme 8. Methylation of perquinoline-substituted HAB 21.
Theoretically, the salt 25 can exist in eight rotameric forms A-H.
2
3
1
3
Similar to hexa(-naphthyl)benzene, solving the simple
combinatoric problem created by propeller-like compounds
such as 21 or 25 results in the following ratio: A:B:C:D:E:F:G:H =
of rotamers (1:0.9) as its non-methylated precursor, and the
corresponding ratio of the salt 24b in DMSO-d is 1:1.27. In
6
1
:6:3:6:6:3:6:1. Figure 2 shows possible interconversions
between the forms A-H, which we calculated in form of the
hexacationic species (DFT, 6-31G*/PBE0). Schematically, the
rotamers can be classified as those in which N-
methylquinolinium residues are 6:0 (all-syn), 5-up/1-down, 4
up/2-down (1,2; 1,3; 1,4), and 3-up/3-down (1,2,3; 1,2,4; 1,3,5)
summary, except for 10a, no spectroscopically detectable
changes of the symmetry of the molecules is caused by the
methylations. On methylation, the UV/Vis absorption maxima
display bathochromic shifts. The spectra are shown in the
Supporting Information.
(Figure 2). The calculated energy differences between the eight
rotamers of 25 are extremely small, and so are the differences
4
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between the rotamers of 21. The lowest energy rotamer of 25
View Article Online
DOI: 10.1039/C9OB00357F
is the 3-up-3-down (1,3,5) isomer, whereas the all-syn isomer
-1
(
6,0) has an energy of 7.65 kJ∙mol and is thus the less stable.
Similarly, the (6,0) rotamer of the neutral precursor 21 is by only
3
.8 kJ∙mol-1 less stable than the (3,3)-1,3,5 rotamer. As a matter
1
of fact, the rotamers of 25 cause signal overlaps in the H NMR
spectrum at ambient temperature (Figure 1, spectrum 1,
Supplementary Information). The spectra change reversibly on
heating of the NMR sample successively from rt to 100 °C
(Figure 1, spectra 2-9); on cooling, the original spectrum is
reconstituted (Figure 1, spectrum 10). Obviously, no other ratio
of sets of isochronous rotamers is formed during this
temperature experiment. Calculations of all true minimum
structures of 25 show that in all rotamers the dihedral angles
between the quinoline and the phenyl rings are in the range
from 71° to 88°.
up
down
down
up
up
up
up
up
up
up
up
up
up
(
4,2)-1,4
A
D
up
up
C
4.71
(6,0) up
up (5,1)
down 2.16
7
.65
B
down
down
up
up
up
down
up
Figure 3. Most stable conformation of 25 (calculated) (above).
HOMO (left) and LUMO (right) of 25 (3,3)-1,3,5.
(3,3)-1,2,4
G
up(4,2)-1,2
down
up
3
.62 up
down 1.70
down
down
up
down
up
Conclusions
up
up
down
down
up
up
up
down
down
down
Series of propeller-shaped quinolinium-substituted benzenes as
well as their electrostatically neutral precursors have been
prepared under variation of the substitution site of the
quinoline ring (2-yl, 3-yl, 4-yl), covering the range from the
monocationic quinolinium-2,3,4,5,6-pentaphenylbenzene to
the hexacationic hexakis(1-methylquinolinium-3-yl)benzene.
The latter can exist in eight different rotamers, the (3,3)-1,3,5-
isomer of which was calculated to be the most stable one. Due
to the propeller-shape geometry which suppresses conjugation
throughout the entire -electron system, the frontier orbitals
are located in the individual quinolinium rings.
up (3,3)-1,2,3
2.32 up (4,2)-1,3
0.00 up (3,3)-1,3,5
3.47
F
E
H
Figure 2. Eight energy-minimized rotamers of 25, showing which
can be directly interconverted by rotation of a single substituent.
Relative energies (in kJ∙mol ) are shown in red boxes.
-1
Figure 3 shows the calculated most stable conformer of 25 and
the HOMO/LUMO profiles of the 25 (3,3)-1,3,5 rotamer. In
contrast to 22b,46 in which the HOMO is separated from the
LUMO, the HOMO (-19.41 eV) as well as LUMO (-15.48 eV) of 25
are located individually on the six N-methylquinolinium-3-yl
residues. Considerable parts of the LUMO are located on the
nitrogen atoms as well as on the C2/C4 carbon atoms of the
Experimental
quinolinium residues, whereas significant parts of the HOMO All reactions were carried out under an atmosphere of nitrogen
are located on their fused benzene rings. The fraction of the in flame or oven-dried glassware. All chemicals were purchased
HOMO located at C3 of the (3,3)-1,3,5- as well as of the all-syn and used without further purification unless otherwise
(6,0) rotamer (c.f. Supplementary Information) is lying in one mentioned. Anhydrous solvents were dried according to
plane and is orientated to the opposite phases of neighboring standard procedures before usage. Melting points are
C3, similar to the in-plane-aromatic stabilizations due to uncorrected and were determined in an apparatus according to
interactions between the in-plane ethynyl -orbitals in Dr. Tottoli (Büchi). The ATR-IR spectra were obtained on a
hexaethynylbenzene.4 This may contribute to the stability of Bruker Alpha in the range of 400 to 4000 cm . H NMR spectra
2
7
-1 1
1
3
5. The frontier orbitals of the neutral precursor 21 are shown were recorded at 600 MHz. C NMR spectra were recorded at
in the Supporting Information.
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. Spectroscopic atom numberings are shown
in the Supporting Information. Signal orientations in DEPT
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
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O rP gl ea na si ce &d Bo i on mo to al e dc juu l sa tr mC ha er mg i ins ts ry
Page 6 of 12
ARTICLE
Journal Name
experiments were described as follows: o = no signal; + = up (CH, = 8.3 Hz, 1H, 3-H), 7.70-7.68 (m, 2H, 2ʹ-H, 6ʹ-H), 7.66 (ddd, J =
View Article Online
DOI: 10.1039/C9OB00357F
CH
3 2
); - = down (CH ). The mass spectra (ESIMS) were measured 1.2, 6.9, 8.1 Hz, 1H, 6-H), 7.53-7.48 (m, 3H, 3ʹ-H, 4ʹ-H, 5ʹ-H) ppm.
1
3
with a Varian 320 MS Triple Quad GC/MS/MS (EIMS) or with an
C NMR (150 MHz, CDCl
3
): 훿 = 147.7 (o, C8a), 142.6 (o, C2),
Agilent LCMSD series HP 1100 with APIES at fragmentor 136.7 (+, C4), 131.9 (+, C2ʹ, C6ʹ), 129.7 (+, C4ʹ), 128.9 (+, C3ʹ, C5ʹ),
voltages as indicated. Samples were sprayed from MeOH at 128.6 (+, C5), 128.0 (+, C8), 127.4 (+, C6), 126.9 (o, C4a), 124.3
4
000 V capillary voltage and fragmentor voltages of 30 V unless (+, C3), 121.2 (o, C1ʹ), 89.5 (o, C), 89.1 (o, C) ppm. IR (ATR):
otherwise noted. The HRMS spectra were obtained with a 3053, 2208, 2161, 1616, 1591, 1552, 1498, 1441, 1425, 1310,
Bruker Impact II, a Bruker Daltonik Tesla-Fourier transform-ion 1295, 1211, 1142, 1115, 1070, 989, 829, 788, 769, 760, 693, 620,
-
1
+
cyclotron resonance mass spectrometer, or with a Waters 548, 526, 478 cm . HRMS (ESI): m/z calcd for C17
H
12N [M + H]
+
Micromass LCT with the direct inlet. Chromatography: The 230.0965, found 230.0969; m/z calcd for C17
H11NNa [M + Na]
reactions were traced by thin layer chromatography with silica 252.0789, found 252.0789.
gel 60 (F254, company MERCK KGAA). For the detection of 3-(Phenylethynyl)quinoline (8b): According to Procedure 1, a
substances, quenching was used at either 254 nm or 366 nm solution of 2.080 g (10.00 mmol) of 3-bromoquinoline 6b, 0.070
with a mercury lamp. The preparative column chromatography g (0.10 mmol) of Pd(PPh
was conducted through silica gel 60 (230 400 mesh) of the 1.071 g (10.50 mmol) of ethynylbenzene 7 in 30 mL of
company MERCK KGAA. Yields are not optimized. anhydrous NEt was heated over the period of 1.5 h under reflux
Calculations: All density-functional theory (DFT)-calculations temperature. Finally, a purification by column chromatography
3 2 2
) Cl , 0.038 g (0.20 mmol) CuI and
3
4
8
were carried out by using the Firefly 8.2.0 QC package, which (petroleum ether: ethyl acetate = 3:1) gave 3-(phenyl-
4
9
is partially based on the GAMESS (US) source code, running on ethynyl)quinoline 8b. Yield 2.290 g, 100%, a white solid, mp 83
1
Linux 2.6.18-238.el5 SMP (x86_64) on five AMD Phenom II X6 °C. H NMR (600 MHz, CDCl
3
): 훿 = 9.00 (d, J = 2.0 Hz, 1H, 2-H),
1
090T processor workstations (Beowulf-cluster) with Infiniband 8.30 (d, J = 2.0 Hz, 1H, 4-H), 8.10 (d, J = 8.3 Hz, 1H, 8-H), 7.79 (d,
interconnect and parallelized with MPICH 1.2.7p1. MM2 J = 8.3 Hz, 1H, 5-H), 7.72 (ddd, J = 1.5, 6.9, 8.3 Hz, 1H, 7-H), 7.63-
optimized structures were used as starting geometries. 7.53 (m, 3H, 6-H, 2ʹ-H, 6ʹ-H), 7.42-7.35 (m, 3H, 3ʹ-H, 4ʹ-H, 5ʹ-H)
1
3
Complete geometry optimizations were carried out on the ppm. C NMR (150 MHz, CDCl
3
): 훿 = 152.1 (+, C2), 146.8 (o,
implemented 6-31G* basis set and with the PBE0 density C8a), 138.3 (+, C4), 131.8 (+, C2ʹ, C6ʹ), 130.1 (+, C7), 129.4 (+,
functional. All calculated structures were proven to be true C8), 128.9 (+, C4ʹ), 128.5 (+, C3ʹ, C5ʹ), 127.6 (+, C6), 127.3 (+, C5),
minima by the absence of imaginary frequencies. Partial 127.3 (o, C4a), 122.6 (o, C1ʹ), 117.5 (o, C3), 92.7 (o, C), 86.7 (o,
5
0
charges were obtained with NBO 5.9 from the results of the C) ppm. IR (ATR): 3008, 2162, 1619, 1599, 1564, 1484, 1443,
DFT calculations. Orbital plots were obtained using Jmol 1409, 1368, 1294, 1196, 1124, 1113, 1072, 980, 905, 860, 784,
-
1
1
4.27.2.
756, 691, 656, 640, 539, 515, 498, 474, 429 cm . HRMS (ESI):
+
m/z calcd for C17
H
11NNa [M + Na] 252.0789, found 252.0796.
4
-(Phenylethynyl)quinoline (8c): According to Procedure 1, a
solution of 0.624 g (3.00 mmol) of 4-bromoquinoline 6c, 0.042
g (0.06 mmol) of Pd(PPh Cl , 0.012 g (0.06 mmol) CuI and
General procedure of Sonogashira-Hagihara coupling 0.367 g (3.6 mmol) of ethynylbenzene 7 in 20 mL of anhydrous
Procedure 1)
NEt was heated over the period of 2 h under reflux
The reactions were carried out under a nitrogen atmosphere. A temperature. Finally, a purification by column chromatography
mixture of 5 mmol of corresponding haloquinoline 1, 1 mol % of (petroleum ether: ethyl acetate 5:1) gave 4-
Pd(PPh Cl
, and 2 mol % of CuI was suspended in 7 mL of dry (phenylethynyl)quinoline 8c. Yield 0.674 g, 98%, of a yellow
NEt with stirring.
ethynylbenzene 2 (1.05 equiv) in dry NEt
Synthesis.
)
3 2
2
(
3
=
)
3 2
2
1
3
): = 8.90 (d, J = 4.4
훿
3
A
sample of the corresponding solid, mp 45 °C. H NMR (600 MHz, CDCl
was added dropwise Hz, 1H, 2-H), 8.38 (ddd, J = 0.6, 1.4, 8.3 Hz, 1H, 5-H), 8.14 (d, J =
3
at ambient temperature. The resulting solutions were then 8.1 Hz, 1H, 8-H), 7.76 (ddd, J = 1.4, 6.9, 8.4 Hz, 1H, 7-H), 7.68-
stirred at reflux temperature until complete conversion was 7.66 (m, 2H, 2ʹ-H, 6ʹ-H), 7.64 (ddd, J = 1.4, 6.9, 8.2 Hz, 1H, 6-H),
monitored by TLC. The mixtures were then allowed to cool to rt. 7.57 (d, J = 4.4 Hz, 1H, 3-H), 7.44-7.42 (m, 3H, 3ʹ-H, 4ʹ-H, 5ʹ-H)
1
3
The solvents were removed in vacuo. The resulting residues ppm. C NMR (150 MHz, CDCl
were finally purified by column chromatography (petroleum C8a), 132.1 (+, C2ʹ, C6ʹ), 130.0 (+, C7, C8), 129.9 (o, C4), 129.5
ether: ethyl acetate) to afford the products.
(+, C4ʹ), 128.7 (+, C3ʹ, C5ʹ), 127.9 (o, C4a), 127.3 (+, C6), 126.1
-(Phenylethynyl)quinoline (8a). According to Procedure 1, a (+, C5), 123.7 (+, C3), 122.4 (o, C1ʹ), 98.8 (o, C), 85.2 (o, C)
solution of 0.491 g (3.00 mmol) of 2-chloroquinoline 6a, 0.042 g ppm. IR (ATR): 3085, 3051, 3029, 2998, 2212, 1961, 1919, 1595,
0.06 mmol) of Pd(PPh Cl
, 0.012 g (0.06 mmol) CuI and 0.367 1576, 1505, 1487, 1441, 1418, 1390, 1363, 1310, 1277, 1217,
g (3.6 mmol) of ethynylbenzene 7 in 20 mL of anhydrous NEt
1192, 1175, 1134, 1068, 1029, 919, 871, 846, 815, 756, 687, 641,
3
): = 149.9 (+, C2), 148.3 (o,
훿
2
(
)
3 2
2
3
-1
was heated over the period of 2 h under reflux temperature. 579, 550, 529, 506, 485, 442 cm . HRMS (ESI): m/z calcd for
+
Finally, a purification by column chromatography (petroleum
17
C H
12N [M + H] 230.0965, found 230.0965.
ether: ethyl acetate = 5:1) gave 2-(phenylethynyl)quinoline 8a. General procedure of preparation of propeller-like
5
1
1
Yield 0.653 g, 95%, a yellow solid, mp 75 °C (72-75 °C ). H NMR compounds (Procedure 2): Benzophenone (10 g) was melted in
600 MHz, CDCl
): 훿 = 8.44 (d, J = 8.3 Hz, 1H, 4-H), 8.03-8.01 (m, a 50 mL round-bottomed flask fitted with an air condenser.
H, 5-H, 8-H), 7.82 (ddd, J = 1.5, 6.7, 8.5 Hz, 1H, 7-H), 7.74 (d, J Corresponding phenylethynylquinoline 8 (2.00 mmol) and
(
3
2
6
| Org. Biomol. Chem. 2018, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
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Page 7 of 12
O rP gl ea na si ce &d Bo i on mo to al e dc juu l sa tr mC ha er mg i ins ts ry
Journal Name
ARTICLE
tetraphenylcyclopentadienone 9 (2.50 mmol) were added to (0.302 g, 1.319 mmol) and tetraphenylcyclopenVtieawdAiertincloenOenlin9e
the flask, which was heated for 0.5 h using a heat gun. The (0.430 g, 1.121 mmol, 0.85 equiv) in benzDoOpIh: 1e0n.1o0n3e9/(C190OgB)00in35570F
solution was cooled to rt and toluene (10 mL) was added to mL round-bottomed flask in 0.5 h (total conversion of dienone).
1
prevent the solidification of the benzophenone. After cooling, Yield 0.529 g, 81%, a white solid, mp 323 °C. H NMR (600 MHz,
n-hexane (50 mL) was added, resulting in the precipitation of a CDCl
3
): 훿 = 8.49 (d, J = 4.4 Hz, 1H, 2-H), 7.86 (dd, J = 0.5, 7.9 Hz,
product, which was collected by vacuum filtration.
1H, 5-H), 7.80 (d, J = 8.3, 1H, 8-H), 7.50 (ddd, J = 1.5, 6.9, 8.4 Hz,
2
,3,4,5,6-Pentaphenyl-1-(quinolin-2-yl)benzene
(10a): 1H, 7-H), 7.39 (ddd, J = 1.3, 6.9, 8.3 Hz, 1H, 6-H), 7.05 (d, J = 4.4
2
,3,4,5,6-pentaphenyl-1-(quinoline-2-yl)benzene 10a was Hz, 1H, 3-H), 6.93-6.82 (m, 17H, Ph), 6.77-6.75 (m, 2H, Ph), 6.68-
1
3
prepared by Procedure 2 using 2-(phenylethynyl)quinoline 8a 6.64 (m, 4H, Ph), 6.55-6.52 (m, 2H, Ph) ppm. C NMR (150 MHz,
(
(
0.158 g, 0.690 mmol) and tetraphenylcyclopentadienone 9 CDCl
0.394 g, 1.035 mmol) in benzophenone (5 g) in 10 mL round- 140.74 (o), 140.70 (o), 140.4 (o), 140.2 (o), 139.7 (o), 136.0 (o,
3
): 훿 = 148.8 (+, C2), 147.9 (o, C4), 147.7 (o, C8a), 141.5 (o),
bottomed flask in 0.75 h. Yield 0.260 g, 64%, a white solid, mp C ), 131.53 (+), 131.46 (+), 131.44 (+), 130.9 (+), 130.2 (+), 129.3
1
>
8
5
7
2
2
6
360 °C. H NMR (600 MHz, CDCl
3
): 훿 = 7.75 (d, J = 8.6 Hz, 1H, (+, C8), 128.8 (+, C7), 128.0 (o, C4a), 127.2 (+, C5), 126.84 (+),
i
i
-H), 7.64 (d, J = 8.5 Hz, 1H, 4 -H), 7.55 (dd, J = 1.2, 8.2 Hz, 1H, 126.81 (+), 126.7 (+), 126.6 (+), 125.8 (+), 125.7 (+, C6), 125.5
-H), 7.51 (ddd, J = 1.5, 6.9, 8.5 Hz, 1H, 7 -H), 7.36 (ddd, J = 1.1, (+), 124.4 (+, C3) ppm. IR (ATR): 3052, 3025, 1598, 1496, 1440,
.0, 8.1 Hz, 1H, 6 -H), 7.01 (d, J = 8.5 Hz, 1H, 3 -H), 7.00-6.96 (m, 1385, 1291, 1071, 1028, 905, 852, 817, 759, 736, 718, 695, 616,
H, Ph), 6.93-6.83 (m, 16 H, 2 -H, 6 -H, 2 -H, 6 -H, 2 -H, 6 -H, 586, 562, 551, 542, 463, 449, 425 cm . HRMS (ESI): m/z calcd
-H, 6 -H, 3 -H, 5 -H, 3 -H, 5 -H, 3 -H, 5 -H, 3 -H, 5 -H), 6.79- for C45
.72 (m, 7H, Ph) ppm. C NMR (150 MHz, CDCl
C2 ), 147.1 (o, C8a ), 141.6 (o, C1 ), 140.8/140.4/140.3/140.1 (o, Procedure 1, a solution of 2.080 g (10.00 mmol) of 3-
C2, C3, C5, C6, C1 , C1 , C1 , C1 ), 140.6 (o, C4), 140.0 (o, C1), bromoquinoline 6b, 0.070 g (0.10 mmol) of Pd(PPh
i
i
i
i
ii
ii
iii
iii
v
v
-1
vi
vi
ii
ii
iii
iii
v
v
vi
vi
+
H
32N [M + H] 586.2530, found 586.2522.
): 훿 = 160.2 (o, 3-((4-Ethynylphenyl)ethynyl)quinoline (14): According to
3
1
3
i
i
iv
ii
iii
v
vi
3 2
) Cl
2
, 0.038
i
i
1
1
(
34.2 (+, C4 ), 131.7/131.5/131.4/130.7 (+, Ph), 129.05 (+, C7 ), g (0.20 mmol) of CuI and 1.197 g (9.50 mmol) of 1,4-
29.00 (+, C8 ), 127.3 (+, C5 ), 126.8 (+, Ph), 126.0 (+, C6 ), 125.7 diethynylbenzene 13 in 50 mL of anhydrous NEt
o, C4a ), 125.51/125.45 (+, Ph) ppm. IR (ATR): 3055, 3025, 1597, (3.5 h) under reflux temperature. Finally, a purification by
i
i
i
3
was heated
i
1
9
558, 1501, 1441, 1403, 1323, 1300, 1221, 1154, 1073, 1029, column chromatography (petroleum ether: ethyl acetate = 3:1)
-1
48, 839, 812, 753, 718, 695, 617, 583, 555, 531, 478 cm . gave 3-((4-ethynylphenyl)ethynyl)quinoline 14. Yield 0.889 g,
+
1
HRMS (ESI): m/z calcd for C45H32N [M + H] 586.2530, found 37%, a brown solid, mp 113 °C. H NMR (600 MHz, CDCl
3
): 훿 =
5
2
2
86.2531.
,3,4,5,6-Pentaphenyl-1-(quinolin-3-yl)benzene
,3,4,5,6-Pentaphenyl-1-(quinoline-3-yl)benzene 10b was 1.5, 7.0, 8.5 Hz, 1H, 7-H), 7.57 (ddd, J = 1.5, 7.0, 8.1 Hz, 1H, 6-H),
8.99 (d, J = 2.1 Hz, 1H, 2-H), 8.30 (d, J = 2.1 Hz, 1H, 4-H), 8.10 (d,
(10b): J = 8.5 Hz, 1H, 8-H), 7.70 (d, J = 8.1 Hz, 1H, 5-H), 7.73 (ddd, J =
prepared by Procedure 2 using 3-(phenylethynyl)quinoline 8b 7.55-7.53 (m, 2H, 2ʹ-H, 6ʹ-H), 7.51-7.49 (m, 2H, 3ʹ-H, 5ʹ-H), 3.20
1
3
(
(
0.458 g, 2.00 mmol) and tetraphenylcyclopentadienone 9 (s, 1H, CCH) ppm. C NMR (150 MHz, CDCl
0.961 g, 2.50 mmol) in benzophenone (10 g) in 50 mL round- 147.1 (o, C8a), 138.5 (+, C4), 132.3 (+, C3ʹ, C5ʹ), 131.7 (+, C2ʹ,
3
): 훿 = 152.1 (+, C2),
bottomed flask in 0.5 h. Yield 0.590 g, 51%, a white solid, mp C6ʹ), 130.4 (+, C7), 129.6 (+, C8), 127.8 (+, C5), 127.5 (+, C6),
1
3
34 °C. H NMR (600 MHz, CDCl
3
): 훿 = 8.45 (d, J = 2 Hz, 1H, 2i- 127.4 (o, C4a), 123.2 (o, C1ʹ), 122.6 (o, C4ʹ), 117.2 (o, C3), 92.1
H), 7.84 (d, J = 8.4 Hz, 1H, 8i-H), 7.59 (d, J = 2 Hz, 1H, 4i-H), 7.53- (o, C), 88.7 (o, C), 83.2 (o, C), 79.4 (o, C) ppm. IR (ATR):
i
i
i
7
.51 (m, 1H, 7 -H), 7.43 (d, J = 8.0 Hz, 5 -H), 7.35-7.33 (m, 1H, 6 - 3265, 3060, 3034, 2101, 1969, 1710, 1699, 1602, 1566, 1487,
ii
ii
iii
iii
iv
iv
v
H), 6.88-6.85 (m, 20H, 2 -H, 6 -H, 2 -H, 6 -H, 2 -H, 6 -H, 2 -H, 1404, 1351, 1266, 1145, 1105, 1010, 981, 958, 906, 861, 838,
-H, 2 -H, 6 -H, 3 -H, 5 -H, 3 -H, 5 -H, 3 -H, 5 -H, 3 -H, 5 -H, 782, 752, 691, 653, 622, 548, 471, 419 cm . HRMS (ESI): m/z
-H, 5 -H), 6.83-6.78 (m, 4H, 4 -H, 4 -H, 4 -H, 4 -H), 6.78-6.77 calcd for C19
m, 1H, 4 -H) ppm. C NMR (150 MHz, CDCl
45.6 (o, C8a ), 141.4 (o, C4), 141.07 (o, C2, C6), 140.88 (o, C3, 1-(Quinolin-3-yl)-2,3,4,5,-tetraphenyl-6-(4-(1,2,3,4-
C5), 140.44 (o, C1 ), 140.34 (o, C1 , C1 ), 139.96 (o, C1 , C1 ), tetraphenyl)phenyl)-benzene (15): 1-(Quinolin-3-yl)-2,3,4,5,-
37.8 (+, C4 ), 136.51 (o, C1), 134.2 (o, C3 ), tetraphenyl-6-(4-(1,2,3,4-tetraphenyl)phenyl)benzene 15 was
31.51/131.48/131.45/131.41/131.37 (+, C2 , C6 , C2 , C6 , prepared
v
vi
vi
ii
ii
iii
iii
iv
iv
v
v
-1
6
3
vi
vi
ii
iii
v
vi
+
H
12N [M + H] 254.0964, found 254.0972; m/z calcd
iv
13
i
+
(
1
3
): 훿 = 152.9 (+, C2 ), for C19
H
11NNa [M + Na] 276.0789, found 276.0785.
i
iv
ii
vi
iii
v
i
i
1
1
ii
ii
iii
iii
by
Procedure
2
using
3-((4-
iv
iv
v
v
vi
vi
i
i
C2 , C6 , C2 , C6 , C2 , C6 ), 129.0 (+, C8 ), 128.9 (+, C7 ), 127.6 ethynylphenyl)ethynyl)quinoline 14 (0.290 g, 1.146 mmol) and
+, C5 ), 127.4/127.0/126.85/126.83/126.78 (+, C3 , C5 , C3 , tetraphenylcyclopentadienone 9 (1.320 g, 3.438 mmol, 3.0
i
ii
ii
iii
(
iii
iv
iv
v
v
vi
vi
i
i
C5 , C3 , C5 , C3 , C5 , C3 , C5 ),127.1 (o, C4a ), 126.2 (+, C6 ), equiv) in benzophenone (10 g) in 50 mL round-bottomed flask
ii
vi
iii
v
iv
1
25.87 (+, C4 , C4 ), 125.54 (+, C4 , C4 ), 125.52 (+, C4 ) ppm. in 0.5 h. Yield 0.885 g, 77%, a brown solid, mp 368 °C (decomp.).
1
IR (ATR): 3055, 3024, 1662, 1600, 1495, 1440, 1401, 1354, 1311,
H NMR (600 MHz, CDCl
3
): 훿 = 8.42 (d, J = 2.0 Hz, 1H), 7.90 (d, J
1
7
275, 1261, 1127, 1070, 1029, 966, 906, 838, 817, 779, 747, 738, = 8.3 Hz, 1H), 7.57 (ddd, J = 1.4, 6.8, 8.3 Hz, 1H), 7.55 (d, J = 2.0
-1
19, 695, 647, 638, 555, 544, 535, 480, 443, 413 cm . HRMS Hz, 1H), 7.46-7.45 (m, 1H), 7.41-7.38 (m, 1H), 7.23 (s, 1H), 7.15-
32N [M + H]+ 586.2529, found 1.13 (m, 2H), 7.07-7.06 (m, 2H), 6.94-6.55 (m, 40H) ppm.
13
C
(APCI): m/z calcd for C45
H
5
2
2
86.2530.
,3,4,5,6-Pentaphenyl-1-(quinolin-4-yl)benzene
,3,4,5,6-Pentaphenyl-1-(quinoline-4-yl)benzene 10c was 140.73 (o), 140.48 (o), 140.43 (o), 140.34 (o), 140.27 (o), 140.21
NMR (150 MHz, CDCl
3
): 훿 = 152.9 (+), 145.7 (o), 141.8 (o), 141.7
(10c): (o), 141.3 (o), 141.1 (o), 140.86 (o), 140.82 (o), 140.80 (o),
prepared by Procedure 2 using 4-(phenylethynyl)quinoline 8c (o), 140.07 (o), 139.95 (o), 139.7 (o), 139.3 (o), 139.1 (o), 138.8
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 7
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O rP gl ea na si ce &d Bo i on mo to al e dc juu l sa tr mC ha er mg i ins ts ry
Page 8 of 12
ARTICLE
Journal Name
(
o), 137.9 (o), 137.8 (+), 136.5 (o), 134.2 (o), 132.5 (+), 131.6 (+), Ethyne-1,2-diyldiquinoline 18a (0.280 g, 1.00 VimewmAroticll)e Oanlninde
1
1
1
1
31.5 (+), 131.39 (+), 131.35 (+), 131.0 (+), 130.9 (+), 130.2 (+), tetraphenyl-cyclopentadienone 9 (0.576DOg,I: 110.5.10039m/Cm9OolB)0w03e5r7eF
30.0 (+), 129.1 (+), 128.89 (+), 128.87 (+), 128.77 (+), 128.4 (+), added to the flask, which was heated for 1 h using an open
27.69 (+), 127.62 (+), 127.3 (+), 127.1 (+), 127.0 (+), 126.96 (o), flame. The solution was cooled to rt and toluene (3 mL) was
26.82 (+), 126.76 (+), 126.66 (+), 126.31 (+), 126.2 (+), 125.8 added to prevent the solidification of the benzophenone. After
(+), 125.64 (+), 125.55 (+), 125.50 (+), 125.46 (+), 125.36 (+) cooling, n-hexane (200 mL) was added, resulting in the
ppm. IR (ATR): 3024, 1599, 1490, 1441, 1398, 1275, 1071, 1021, precipitation of 19a as a white powder, which was washed with
-
1
9
07, 851, 763, 696, 638, 615, 566, 554, 480, 425 cm . HRMS n-hexane and toluene, and collected by vacuum filtration. Yield
+
1
(ESI): m/z calcd for C75
H
51NNa [M + Na] 988.3914, found 0.570 g, 90%, a white solid, mp 344 °C. H NMR (600 MHz,
9
3
1
0
88.3901.
DMSO-d
6
), two sets of isochronous rotameric forms (1:0.8): 훿 =
,3'-Ethyne-1,2-diyldiquinoline (18a): According to Procedure 8.52 (d, J = 2.1 Hz, 3.6H, 2-H, 2ʹ-H), 7.97 (d, J = 1.7 Hz, 2H, 4-H),
, a solution of 0.208 g (1.00 mmol) of 3-bromoquinoline 6b, 7.93 (d, J = 1.7 Hz, 1.6H, 4ʹ-H), 7.64-7.61 (m, 3.6H, 8-H, 8ʹ-H),
3 2 2
.007 g (0.01 mmol) of Pd(PPh ) Cl , 0.0038 g (0.02 mmol) CuI 7.59 (d, J = 7.9 Hz, 2H, 5-H), 7.52 (d, J = 8.3 Hz, 1.6H, 5ʹ-H), 7.50-
and 0.2184 g (1.05 mmol) of 3-ethynylquinoline 17 in 10 mL of 7.47 (m, 3.6H, 7-H, 7ʹ-H), 7.38-7.36 (m, 2H, 6-H), 7.35-7.32 (m,
1
3
anhydrous NEt
3
was heated (2 h) under reflux temperature. 1.6H, 6ʹ-H), 7.01-6.74 (m, 36H, Ph) ppm. C NMR (150 MHz,
): 훿 = 152.0 (+, C2), 151.8 (+, C2ʹ), 144.99 (o, C8aʹ),
Finally, a purification by column chromatography (petroleum DMSO-d
6
ether: ethyl acetate = 3:1) gave 3,3'-ethyne-1,2-diyldiquinoline 144.98 (o, C8), 141.06 (o), 141.04 (o), 140.9 (o), 139.5 (o),
1
1
8a. Yield 0.196 g, 70%, a brownish solid, mp 173 °C. H NMR 139.29 (o), 139.25 (o), 137.4 (+, C4ʹ), 137.0 (+, C4), 136.95 (o,
(
=
600 MHz, CDCl
3
): 훿 = 9.05 (d, J = 2 Hz, 2H, 2-H, 2ʹ-H), 8.36 (d, J C), 136.93 (o, C), 132.97 (o), 132.94 (o), 130.93 (+), 130.89(+),
2 Hz, 2H, 4-H, 4ʹ-H), 8.12 (d, J = 8.1 Hz, 2H, 8-H, 8ʹ-H), 7.82 (d, 130.77 (+), 130.72 (+), 130.70 (+), 129,66 (+), 129.51 (+), 129.18
J = 8.3 Hz, 2H, 5-H, 5ʹ-H), 7.74 (ddd, J = 1.4, 6.9, 8.4 Hz, 2H, 7-H, (+, C7 or C7ʹ), 129.16 (+, C7 or C7ʹ), 128.34 (+, C8 or C8ʹ), 128.31
1
3
7
(
1
ʹ-H) 7.58 (ddd, J = 1.1, 6.9, 8.0 Hz, 2H, 6-H, 6ʹ-H) ppm. C NMR (+, C8 or C8ʹ), 127.8 (+, C5), 127.6 (+, C5ʹ), 127.0 (+), 126.8 (+),
150 MHz, CDCl
): 훿 = 152.0 (+, C2, C2ʹ), 147.2 (o, C8a, C8aʹ), 126.7 (+), 126.5 (+, C6, C6ʹ), 126.3 (o, C4a or C4aʹ), 126.20 (o,
38.8 (+, C4, C4ʹ), 130.5 (+, C7, C7ʹ), 129.6 (+, C8, C8ʹ), 127.8 (+, C4a or C4aʹ), 125.9 (+), 125.7 (+) ppm. IR (ATR): 3055, 3025,
3
C5, C5ʹ), 127.6 (+, C6, C6ʹ), 127.3 (o, C4a, C4aʹ), 116.9 (o, C3, C3ʹ), 1600, 1552, 1490, 1401, 1314, 1241, 1127, 1071, 966, 907, 812,
-
1
9
1
8
4
0.0 (o, C) ppm. IR (ATR): 3061, 2169, 1839, 1616, 1565, 1487, 784, 747, 696, 632, 536, 476 cm . HRMS (ESI): m/z calcd for
+
468, 1413, 1357, 1291, 1226, 1192, 1122, 991, 955, 906, 878,
C H N
48 33 2
[M + H] 637.2639, found 637.2637.
69, 786, 770, 761, 748, 737, 640, 614, 594, 553, 527, 491, 479, 1-(Quinolin-3-yl)-2-(quinolin-4-yl)-3,4,5,6-tetraphenylbenzene
-
1
+
72, 461, 445, 415 cm . MS (ESI): m/z = 281.1 [M + H] . HRMS (19b):
1-(Quinoline-3-yl)-2-(quinoline-4-yl)-3,4,5,6-
[M + H] 281.1074, found 281.1072. tetraphenylbenzene 19b was prepared by Procedure 2 using 4-
+
(ESI): m/z calcd for C20
H
13
N
2
3
-(Quinolin-4-ylethynyl)quinoline (18b): According to (quinolin-3-ylethynyl)quinoline 18b (0.264 g, 0.943 mmol) and
Procedure 1, a solution of 0.208 g (1.00 mmol) of 4- tetraphenylcyclopentadienone 9 (0.543 g, 1.414 mmol) in
bromoquinoline 6c, 0.070 g (0.10 mmol) of Pd(PPh Cl , 0.038 benzophenone (5 g) in 10 mL round-bottomed flask in 0.5 h. The
g (0.20 mmol) CuI and 0.218 g (1.05 mmol) of 3- solution was cooled to rt and toluene (4 mL) was added to
ethynylquinoline 17 in 10 mL of anhydrous NEt was heated (3.5 prevent the solidification of the benzophenone. Then solvents
)
3 2
2
3
h) under reflux temperature. Finally, a purification by column were evaporated with silica gel and obtained solid was purified
chromatography (petroleum ether: ethyl acetate = 3:1) gave 3- by column chromatography with EE:PE (1:1) as eluents to give
1
(
quinolin-4-ylethynyl)quinoline 18b. Yield 0.160 g, 57%, a yellow 19b. Yield 0.469 g, 78%, a white solid, mp 300 °C (decomp.). H
1
solid, mp 134 °C. H NMR (600 MHz, CDCl
3
): 훿 = 9.11 (d, J = 2.1 NMR (600 MHz, DMSO-d
6
): 훿 = 8.58 (d, J = 2.2 Hz, 1H), 8.46-8.44
Hz, 1H, 2-H), 8.94 (d, J = 4.5 Hz, 1H, 2ʹ-H), 8.45 (d, J = 2.0 Hz, 1H, (m, 2H), 8.25 (d, J = 2.2 Hz, 1H), 7.97-7.96 (m, 1H), 7.91-7.87 (m,
4
8
7
7
6
-H), 8.40 (dd, J = 0.9, 8.3 Hz, 1H, 5ʹ-H) 8.16 (d, J = 7.8, 1H, 8ʹ-H), 2H), 7.61-7.49 (m, 10H), 7.47 (ddd, J = 1.6, 6.8, 8.4 Hz, 2H), 7.45
.14 (d, J = 7.8 Hz, 1H, 8-H) 7.85 (d, J = 7.9 Hz, 1H, 4-H), 7.80– (ddd, J = 1.5, 6.6, 8.2 Hz, 1H), 7.41-7.39 (m, 2H), 7.36 (ddd, J =
.76 (m, 2H, 7-H, 7ʹ-H), 7.68 (ddd, J = 1.2, 6.9, 8.2 Hz, 1H, 6ʹ-H), 1.2, 6.8, 8.1 Hz, 1H), 7.26-7.24 (m, 1H), 7.21-7.19 (m, 1H), 7.13-
.63 (d, J = 4.3 Hz, 1H, 3ʹ-H), 7.61 (ddd, J = 1.2, 7.1, 8.2 Hz, 1H, 7.00 (m, 8H), 6.96-6.81 (m, 22H), 6.79-6.72 (m, 3H), 6.71-6.67
1
3
13
-H) ppm. C NMR (150 MHz, CDCl
3
): 훿 = 151.9 (+, C2), 149.9 (+, (m, 4H), 6.55 (t, J = 7.6 Hz, 2H) ppm. C NMR (150 MHz, DMSO-
): 훿 = 151.50 (+), 150.81 (+), 148.76 (+), 148.58 (+), 146.85 (o),
30.2 (+, C7ʹ), 130.2 (+, C8ʹ), 129.7 (+, C8), 129.1 (o, C4ʹ), 127.9 146.78 (o) ,145.98 (o), 145.89 (o), 145.00 (o), 144.90 (o), 141.21
+, C5), 127.7 (+, C6), 127.6 (o, C4aʹ), 127.6 (+, C6ʹ), 127.3 (o, (o), 141.18 (o), 141.07 (o), 141.01 (o), 140.86 (o), 140.70 (o),
C4a), 126.0 (+, C5ʹ), 123.9 (+, C3ʹ), 116.5 (o, C3), 95.7 (o, C), 140.29 (o), 140.20 (o), 139.52 (o), 139.45 (o), 139.17 (o), 139.15
C2ʹ), 148.3 (o, C8aʹ), 147.5 (o, C8a), 139.2 (+, C4), 130.9 (+, C7),
1
(
d
6
8
1
6
+
8.3 (o, C) ppm. IR (ATR): 3033, 2209, 2203, 1615, 1572, 1484, (o), 139.05 (o), 138.94 (o), 136.72 (+), 136.35 (o), 136.29 (o),
419, 1282, 1220, 1192, 1123, 1011, 976, 905, 845, 787, 758, 135.89 (o), 135.82 (o), 135.61 (+), 132.66 (o), 132.55 (o), 131.11
-1
51, 609, 542, 514, 491, 476, 445 cm . MS (ESI): m/z = 281.1 [M (+), 130.98 (+), 130.94 (+), 130.90 (+), 130.81 (+), 130.76 (+),
+
+
H] . HRMS (ESI): m/z calcd for C20
H N
13 2
[M + H] 281.1074, 130.71 (+), 130.63 (+), 130.60 (+), 130.58 (+), 130.53 (+), 130.42
found 281.1062.
,2-Di(quinolin-3-yl)-3,4,5,6-tetraphenylbenzene
According to Procedure 2, benzophenone (5 g) was melted in a (+), 126.81 (+), 126.76 (+), 126.72 (+), 126.67 (+), 126.63 (+),
(+), 129.36 (+), 129.07 (+), 129.01 (+), 128.95 (+), 128.75 (+),
1
(19a): 128.68 (+), 128.21 (+), 127.63 (+), 127.31 (+), 126.93 (+), 126.89
5
0 mL round-bottomed flask fitted with an air condenser. 3,3'- 126.49 (+), 126.45 (+), 126.40 (+), 126.33 (+), 126.24 (+), 125.89
8
| Org. Biomol. Chem. 2018, 00, 1-3
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Page 9 of 12
O rP gl ea na si ce &d Bo i on mo to al e dc juu l sa tr mC ha er mg i ins ts ry
Journal Name
ARTICLE
(
+), 125.83 (+), 125.73 (+), 125.65 (+), 124.37 (+), 123.82 (+) (ATR): 3025, 1619, 1602, 1567, 1489, 1355, 1317, 1260, 1195,
View Article Online
DOI: 10.1039/C9OB00357F
ppm. IR (ATR): 3055, 3027, 1699, 1600, 1585, 1567, 1505, 1490, 1126, 1110, 1043, 1017, 974, 953, 905, 858, 785, 744, 696, 605,
1
7
-1
36 6
463, 1442, 1384, 1359, 1126, 1072, 1027, 965, 908, 854, 814, 527, 474, 439 cm . HRMS (ESI): m/z calcd for C60H N Na [M +
-
1
+
61, 696, 617, 533, 480 cm . HRMS (ESI): m/z calcd for C48
H N
33 2
Na] 863.2899, found 863.2896.
General procedure for the preparation of the salts (Procedure
+
[
M + H] 637.2639, found 637.2629.
General procedure for the synthesis of substituted benzenes 4): Samples of 0.50 mmol of the corresponding quinolines were
Procedure 3) 2-(Phenylethynyl)quinoline 8a (0.21 g, 0.92 dissolved in toluene containing 1 drop of nitrobenzene. Then
(
mmol) was dissolved in anhydrous dioxane (4 mL) in an oven 0.75 mmol of dimethyl sulfate was added with stirring.
dried Schlenk flask under a nitrogen atmosphere and the flask Thereafter the resulting mixture was stirred under reflux
was evacuated and filled with nitrogen repeatedly (3×). Then, temperature. After completion of the reaction (controlled by
Co (CO) (0.015 g) was added to the flask under a nitrogen TLC), the solution was cooled, the crude product was filtered
2 8
atmosphere and the flask was evacuated and filled with off, washed with ethyl acetate (3×10 mL), and dried to afford
nitrogen again (3×). The resulting mixture was refluxed for 14 h the product.
and dioxane was evaporated. The resulting residue was 2,3,4,5,6-Pentaphenyl-1-(1-methylquinolinium-2-yl)benzene
dissolved in dichloromethane and filtered through a short pad methylsulfate (22a): According to Procedure 4, a solution of
of silica gel. Evaporation of the solvent afforded a dark colored 0.100 g (0.171 mmol) of 2,3,4,5,6-pentaphenyl-1-(quinoline-2-
solid which was purified by column chromatography with PE - yl)benzene 10a, 1 drop of nitrobenzene and 0.06 mL (0.63
EE as an eluent.
mmol) of dimethyl sulfate in 5 mL of anhydrous toluene was
1
0
,3,5-Triphenyl-2,4,6-tri(quinolin-2-yl)benzene (20a): Yield heated for 2 h under reflux temperature to give 2,3,4,5,6-
1
.021 g, 10%, a white solid, mp 337 °C. H NMR (600 MHz, pentaphenyl-1-(1-methylquinolinium-2-yl)benzene
): 훿 = 7.83 (d, J = 8.5 Hz, 3H, 4ʹ-H), 7.72 (d, J = 8.5 Hz, methylsulfate 22a. Yield 0.115 g, 95%, a white solid, mp 190 °C.
DMSO-d
H, 8ʹ-H), 7.67 (d, J = 7.9 Hz, 3H, 5ʹ-H), 7.57 (t, J = 7.3 Hz, 3H, 7ʹ-
6
1
i
3
H NMR (600 MHz, DMSO-d
6
): 훿 = 8.88 (d, J = 8.5 Hz, 1H, 4 -H),
i
i
i
H), 7.41 (t, J = 7.3 Hz, 3H, 6ʹ-H), 7.22 (d, J = 8.5 Hz, 3H, 3ʹ-H), 7.05 8.31 (d, J = 9.0 Hz, 1H, 8 -H), 8.24-8.23 (m, 2H, 3 -H, 5 -H), 8.14
i
i
(br s, 6H, 2ʹʹ-H, 6ʹʹ-H), 6.70 (br s, 6H, 3ʹʹ-H, 5ʹʹ-H), 6.63 (t, J = 7.3 (t, J = 8.0 Hz, 7 -H), 7.93 (t, J = 7.4 Hz, 6 -H), 7.10-6.84 (m, 25H,
1
3
i
13
Hz, 3H, 4ʹʹ-H) ppm. C NMR (150 MHz, DMSO-d
C2ʹ), 146.4 (o, 8aʹ), 139.9 (o, C2, C4; C6), 139.8 (o, C1, C3, C5), MHz, DMSO-d
1
6
): 훿 = 158.9 (o, Ph), 4.41 (s, 3H, N CH
3
), 3.38 (s, 3H, CH
3
SO
4
) ppm. C NMR (150
i
i
): 훿 = 159.1 (o, C2 ), 144.2 (+, C4 ), 143.9 (o, C1),
6
i
38.7 (o, C1ʹʹ), 134.1 (+, C4ʹ), 130.6 (+,C2ʹʹ, C6ʹʹ) 129.0 (+, C7ʹ), 141.2 (o), 139.1 (o), 138.9 (o), 138.3 (o), 137.5 (o, C8a ), 137.4
28.6 (+, C8ʹ), 127.4 (+, C5ʹ), 126.3 (+, C3ʹʹ, C5ʹʹ), 126.1 (+, C6ʹ), (o), 136.0 (+, C7 ), 131.7 (+), 130.9 (+), 130.6 (+), 130.4 (+), 130.4
25.8 (+, C4ʹʹ), 125.4 (o, C4aʹ), 124.2 (+, C3ʹ) ppm. IR (ATR): 3058, (+, C6 ), 130.3 (+, C5 ), 130.26 (+), 130.0 (+), 129.3 (+), 126.7 (+),
038, 3007, 1617, 1595, 1557, 1501, 1443, 1424, 1332, 1305, 127.43 (o, C4a ), 127.39 (+, C3 ), 127.2 (+), 126.95 (+), 126.91 (+),
253, 1223, 1156, 1139, 1113, 1073, 1031, 959, 906, 838, 753, 126.86 (+), 126.2 (+), 126.0 (+), 119.1 (+, C8 ), 52.8 (+, CH
98, 619, 587, 515, 476, 431, 423, 412 cm . MS (ESI): m/z = 42.5 (+, N CH
88.5 [M + H] . HRMS (ESI): m/z calcd for C51
88.2745, found 688.2743.
i
1
i
i
1
3
1
6
6
6
1
0
i
i
i
3
SO
4
),
-1
i
3
) ppm. IR (ATR): 3056, 3023, 1619, 1600, 1577,
1519, 1497, 1442, 1409, 1347, 1252, 1224, 1176, 1152, 1073,
1059, 1013, 918, 849, 817, 770, 756, 723, 698, 644, 608, 576,
+
+
H N
34 3
[M + H]
-1
+
,2,4-Triphenyl-3,5,6-tri(quinolin-2-yl)benzene (20b): Yield 554, 532, 428 cm . HRMS (ESI): m/z calcd for C46
.063 g, 30%, a white solid, mp 318 °C. H NMR (600 MHz, 600.2686, found 600.2692.
H34N [M]
1
DMSO-d
7
3
6
): 훿 = 7.85 (d, J = 7.5 Hz, 1H), 7.76-7.68 (m, 4H), 7.57- 2,3,4,5,6-Pentaphenyl-1-(1-methylquinolinium-3-yl)benzene
.53 (m, 5H), 7.45-7.42 (m, 3H), 7.32-7.29 (m, 2H), 7.22-7,20 (m, methylsulfate (22b): According to Procedure 4, a solution of
1
3
H), 7.04-6.99 (m, 6H), 6.83-6.67 (m, 9H) ppm. C NMR (150 0.100 g (0.171 mmol) of 2,3,4,5,6-pentaphenyl-1-(quinoline-3-
): 훿 = 159.1 (o), 159.0 (o), 158.8 (o), 146.4 (o), yl)benzene 10b, 1 drop of nitrobenzene and 0.06 mL (0.63
46.3 (o), 146.2 (o), 140.5 (o), 140.4 (o), 140.2 (o), 139.8 (o), mmol) of dimethyl sulfate in 5 mL of anhydrous toluene was
39.6 (o), 139.3 (o), 139.0 (o), 138.9 (o), 138.6 (o), 134.1 (+), heated for 2 h under reflux temperature to give 2,3,4,5,6-
33.6 (+), 130.8 (+), 130.3 (br, +), 129.0 (+), 128.8 (+), 128.6 (+), pentaphenyl-1-(1-methylquinolinium-3-yl)benzene methyl-
MHz, DMSO-d
6
1
1
1
1
1
28.3 (+), 127.4 (+), 127.3 (+), 126.6 (+), 126.5 (+), 126.1 (+), sulfate 22b. Yield 0.122 g, 99%, a light green solid, mp 321 °C
1
25.92 (+), 125.85 (+), 125.81 (+), 125.7 (+), 125.3 (o), 125.2 (o), (decomp.). H NMR (600 MHz, DMSO-d
6
): 훿 = 9.35 (d, J = 1.4 Hz,
1
1
1
4
24.3 (+), 124.2 (+) ppm. IR (ATR): 3056, 3023, 1737, 1597, 1559, 1H, 2-H), 8.84 (s, 1H, 4-H), 8.24 (d, J = 8.1 Hz, 1H, 8-H), 8.14 (ddd,
501, 1441, 1424, 1294, 1160, 1142, 1294, 1160, 1142, 1111, J = 1.5, 7.1, 8.8 Hz, 1H, 7-H), 8.06 (dd, J = 1.1, 8.4 Hz, 1H, 5-H),
072, 1029, 942, 849, 835, 818, 751, 722, 699, 606, 531, 514, 7.92-7.90 (m, 1H, 6-H), 7.05 (d, J = 7.7 Hz, 2H, Ph), 7.02 (d, J =
-1
+
79, 423, 417 cm . MS (ESI): m/z = 688.3 [M + H] . HRMS (ESI): 7.7 Hz, 2H, Ph), 6.96-6.82 (m, 21H, Ph), 4.34 (s, 3H, NCH
3
), 3.37
+
13
m/z calcd for C51
H N
34 3
[M + H] 688.2745, found 688.2739.
(s, 3H, CH SO ) ppm. C NMR (150 MHz, DMSO-d
3 4 6
): 훿 = 150.6
Hexakis(quinolin-3-yl)benzene (21): Hexakis(quinoline-3- (+, C2), 147.5 (+, C4), 142.3 (o), 140.7 (o), 140.5 (o), 139.3 (o),
yl)benzene 11 was prepared by an identical procedure 139.0 (o), 138.4 (o), 135.53 (o, C8a), 135.48 (+, C7), 134.4 (o,
(
Procedure 3) using bis(quinoline-3-yl)acetylene 18a (0.295 g, C3), 132.8 (o, C1ʹ), 131.0 (+), 130.7 (+), 130.64 (+), 130.60 (+),
.35 mmol) as above. A dark colored solid was purified by 130.54 (+), 130.5 (+, C6), 129.9 (+, C5), 127.7 (o, C4a), 127.4 (o),
column chromatography with EE, then MeOH - CHCl (1 : 3) as 126.89 (+), 126.87 (+), 126.80 (+), 126.77 (+), 126.4 (+), 125.92
eluents. Yield 0.295 g, 85%, a white solid, mp >370 °C. The (+), 125.85 (+), 118.9 (+, C8), 52.8 (+, CH SO ), 44.8 (+, NCH
compound is insoluble in all NMR solvents which we tested. IR ppm. IR (ATR): 3051, 3023, 2961, 1600, 1524, 1496, 1442, 1378,
0
3
3
4
3
)
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J. Name., 2013, 00, 1-3 | 9
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O rP gl ea na si ce &d Bo i on mo to al e dc juu l sa tr mC ha er mg i ins ts ry
Page 10 of 12
ARTICLE
Journal Name
-
1
-1
+
1
254, 1215, 1063, 1012, 760, 697, 618, 577, 558, 441 cm . 697, 565, 496, 432 cm . HRMS (ESI): m/z calcd for C76H54N [M]
View Article Online
DOI: 10.1039/C9OB00357F
HRMS (ESI): m/z calcd for C46
H
34N [M]+ 600.2686, found 980.4251, found 980.4257.
6
2
00.2687.
1-(1-Methylquinolinium-3-yl)-2,3,4,5,-tetraphenyl-6-(4-
(1,2,3,4-tetraphenyl)phenyl)benzene hexafluorophosphate
): A suspension of 0.050 g (0.046 mmol) of 1-(1-
.154 g (0.263 mmol) of 2,3,4,5,6 pentaphenyl-1-(quinoline-4- methylquinolinium-3-yl)-2,3,4,5,-tetraphenyl-6-(4-(1,2,3,4-
yl)benzene 10c, 1 drop of nitrobenzene and 0.06 mL (0.63 tetraphenyl)phenyl)benzene methylsulfate 23 and 0.008 g
mmol) of dimethyl sulfate in 5 mL of anhydrous toluene was (0.049 mmol) of NH PF in 4 mL of water was stirred for 1 day
heated for 2 h under reflux temperature to give 2,3,4,5,6- at rt to give 1-(1-methylquinolinium-3-yl)-2,3,4,5,-tetraphenyl-
pentaphenyl-1-(1-methylquinolinium-4-yl)benzene 6-(4-(1,2,3,4-tetraphenyl)phenyl)benzene
methylsulfate 22c. Yield 0.185 g, 99%, a brownish solid, mp 355 hexafluorophosphate 23PF . Yield 0.049 g, 95%, a yellow solid,
): 훿 = 9.14 (d, J = 6.0 mp 220 °C (decomp.). H NMR (600 MHz, DMSO-d ): 훿 = 9.28 (s,
,3,4,5,6-Pentaphenyl-1-(1-methylquinolinium-4-yl)benzene
methylsulfate (22c): According to Procedure 4, a solution of (23PF
0
6
4
6
6
1
1
°
C (decomp.). H NMR (600 MHz, DMSO-d
6
6
Hz, 1H, 2-H), 8.27 (dd, J = 1.0, 8.4 Hz, 1H, 5-H), 8.20 (d, J = 8.9 1H, Q), 8.73 (s, 1H, Q), 8.35 (d, J = 8.9 Hz, 1H, Q), 8.20 (t, J = 7.7
Hz, 1H, 8-H), 8.15 (d, J = 6.0 Hz, 1H, 3-H), 8.11 (ddd, J = 1.4, 7.1, Hz, 1H, Q), 8.05 (d, J = 7.9 Hz, 1H, Q), 7.96 (t, J = 7.5 Hz, 1H, Q),
8
.7 Hz, 1H, 7-H), 7.96-7.94 (m, 1H, 6-H), 7.06 (d, J = 7.7 Hz, 2H, 7.26 (m, 1H, Ph), 7.17-7.14 (m, 4H, Ph), 7.02-6.47 (m, 40H, Ph),
1
3
3 6
Ph), 7.01 (d, J = 7.7 Hz, 2H, Ph), 6.95-6.83 (m, 14H, Ph), 6.74-6.71 4.33 (s, 3H, NCH ) ppm. C NMR (150 MHz, DMSO-d
): 훿 = 150.6
(
3
m, 4H, Ph), 6.60-6.57 (m, 2H, Ph), 4.42 (s, 3H, NCH
H, CH SO
) ppm. 13C NMR (150 MHz, DMSO-d
): 훿 = 158.5 (o, 140.4 (o), 140.3 (o), 140.0 (o), 139.6 (o), 139.3 (o), 139.01 (o),
C4), 147.5 (+, C2), 142.3 (o), 140.6 (o), 139.36 (o), 139.34 (o), 139.00 (o), 138.96 (o), 138.8 (o), 138.6 (o), 138.4 (o), 137.3 (o),
3
), 3.37 (s, (+), 147.5 (+), 142.2 (o), 141.5 (o), 140.9 (o), 140.7 (o), 140.6 (o),
3
4
6
1
1
38.9 (o), 138.3 (o), 137.1 (o, C8a), 135.2 (+, C7), 133.1 (o, C), 136.5 (o), 135.6 (o), 135.5 (+), 134.4 (o), 132.8 (o), 131.0 (+),
31.0 (+), 130.8 (+), 130.52 (+), 130.49 (+), 129.83 (+, C6), 128.80 130.9 (+), 130.8 (+), 130.7 (+), 130.64 (+), 130.60 (+), 130.55 (+),
(
(
+), 129.3 (+, C5), 128.3 (o, C4a), 126.83 (+), 126.78 (+), 126.74 130.53 (+), 130.44 (+), 130.36 (+), 130.28 (+), 130.0 (+), 129.4
+), 126.71 (+), 126.67 (+), 126.4 (+), 125.81 (+), 125.77 (+), (+), 128.9 (+), 128.6 (+), 128.4 (+), 128.2 (+), 127.73 (+), 127.66
1
25.3 (+, C3), 118.8 (+, C8), 52.8 (+, CH
3 4 3
SO ), 45.0 (+, NCH ) ppm. (+), 127.4 (+), 126.85 (+), 126.81 (+), 126.51 (+), 126.46 (+),
IR (ATR): 3051, 3025, 1622, 1615, 1599, 1586, 1577, 1531, 1495, 126.4 (+), 125.91 (+), 125.85 (+), 125.8 (+), 125.44 (+), 125.37
1
8
441, 1401, 1389, 1375, 1335, 1265, 1216, 1118, 1059, 1015, (+), 125.31 (+), 118.9 (+), 44.8 (+) ppm. IR (ATR): 3055, 3027,
-1
69, 820, 766, 726, 695, 609, 576, 553, 542, 464, 430 cm . 1600, 1521, 1495, 1442, 1379, 1072, 1028, 835, 766, 697, 557,
34N [M]+ 600.2686, found 427 cm . HRMS (ESI): m/z calcd for C76
-1
H
54N [M] 980.4251,
+
HRMS (ESI): m/z calcd for C46
H
6
1
00.2673.
-(1-Methylquinolinium-3-yl)-2,3,4,5,-tetraphenyl-6-(4-
found 980.4238.
1,2-Di(1-methylquinolinium-3-yl)-3,4,5,6-tetraphenylbenzene
(
1,2,3,4-tetraphenyl)-phenyl)benzene methylsulfate (23): dihexafluorophosphate (24a): A solution of 0.050 g (0.079
According to Procedure 4, a solution of 0.481 g (0.5 mmol) of 1- mmol) of 1,2-di(quinoline-3-yl)-3,4,5,6-tetraphenylbenzene
quinolin-3-yl)-2,3,4,5,-tetraphenyl-6-(4-(1,2,3,4- 19a, 1 drop of nitrobenzene and 0.02 mL (0.21 mmol) of
tetraphenyl)phenyl)benzene 15, 1 drop of nitrobenzene and dimethyl sulfate in 5 mL of anhydrous toluene was heated for 3
.06 mL (0.63 mmol) of dimethyl sulfate in 5 mL of anhydrous h under reflux temperature, cooled to rt and extracted with
toluene was heated for 2 h under reflux temperature to give 1- water (3×5 mL) and precipitated with excess of NH PF (1.3
1-methylquinolinium-3-yl)-2,3,4,5,-tetraphenyl-6-(4-(1,2,3,4- equiv) to give 1,2-di(1-methylquinolinium-3-yl)-3,4,5,6-
tetraphenyl)phenyl)benzene methylsulfate 23. Yield 0.521 g, tetraphenylbenzene dihexafluorophosphate 24a. Yield 0.068 g,
(
0
4
6
(
1
1
9
6%, a khaki solid, mp 222 °C (decomp.). H NMR (600 MHz, 90%, a white solid, mp 240 °C. H NMR (600 MHz, DMSO-d
DMSO-d
): 훿 = 9.28 (d, J = 1.3 Hz, 1H, Q), 8.73 (s, 1H, Q), 8.35 (d, two sets of isochronous rotameric forms (0.9:1).: 훿 = 9.43 (d, J =
J = 6.7 Hz, 1H, Q), 8.20 (ddd. J = 1.6, 7.0, 8.7 Hz, 1H, Q), 8.05- 1.3 Hz, 0.9H, 2-H), 9.40 (d, J = 1.3Hz, 1H, 2ʹ-H), 9.05 (s, 1H, 4ʹ-H),
6
),
6
8
7
.04 (m, 1H, Q), 7.98-7.95 (m, 1H, Q), 7.26-7.23 (m, 1H, Ph), 8.88 (s, 0.9H, 4-H), 8.30 (d, J = 8.8 Hz, 1H, 8ʹ-H), 8.27 (d, J = 8.9
.19-7.13 (m, 4H, Ph), 7.02-6.99 (m, 3H, Ph), 6.95-6.74 (m, 28H, Hz, 0.9H, 8ʹ-H), 8.16-8.09 (m, 3.8H, 5-H, 5ʹ-H, 7-H, 7ʹ-H), 7.93-
Ph), 6.71-6.64 (m, 5H, Ph), 6.61-6.53 (m, 3H, Ph), 6.49-6.47 (m, 7.90 (m, 1.9H, 6-H, 6ʹ-H), 7.05-6.84 (m, 48H, Ph), 4.38 (s, 6H,
1
3
13
1
(
(
H, Ph), 4.33 (s, 3H, NCH
150 MHz, DMSO-d
): 훿 = 150.6 (+), 147.5 (+), 142.2 (o), 141.5 훿 = 150.6 (+, C2), 149.8 (+, C2ʹ), 147.9 (+, C4ʹ), 147.6 (+, C4),
o), 140.9 (o), 140.7 (o), 140.6 (o), 140.4 (o), 140.3 (o), 140.0 (o), 142.8 (o), 142.7 (o), 141.9 (o), 141.8 (o), 138.5 (o), 137.6 (o),
3 3 4 3 3 6
), 3.36 (s, 3H, CH SO ) ppm. C NMR NʹCH ), 4.32 (s, 5.4H, NCH ) ppm. C NMR (150 MHz, DMSO-d ):
6
1
1
1
1
39.6 (o), 139.3 (o), 139.01 (o), 139.00 (o), 138.96 (o), 138.8 (o), 136.5 (o, C8aʹ), 136.4 (o, C8a), 135.94 (+, C7 or C7ʹ), 135.85 (+,
38.6 (o), 138.4 (o), 137.3 (o), 136.5 (o), 135.6 (o), 135.5 (+), C7 or C7ʹ), 133.10 (o, C), 132.99 (o, C), 132.4 (o), 132.2 (o),
34.4 (o), 132.8 (o), 131.0 (+), 130.9 (+), 130.8 (+), 130.7 (+), 130.89 (+) , 130.75 (+), 130.69 (+), 130.60 (+), 130.48 (+), 130.44
30.64 (+), 130.60 (+), 130.55 (+), 130.53 (+), 130.44 (+), 130.36 (+), 130.42 (+), 130.38 (+), 130.33 (+), 130.31 (+), 130.22 (+, C5),
(
(
+), 130.28 (+), 130.0 (+), 129.4 (+), 128.9 (+), 128.6 (+), 128.4 130.07 (+, C5ʹ), 127.92 (o, C4aʹ), 127.89 (o, C4a), 127.6 (+), 127.0
+), 128.2 (+), 127.73 (+), 127.66 (+), 127.4 (+), 126.85 (+), (+), 126.7 (+), 126.3 (+), 119.00 (+, C8ʹ), 118.90 (+, C8), 45.4 (+,
1
3 3
26.81 (+), 126.51 (+), 126.46 (+), 126.4 (+), 125.91 (+), 125.85 NʹCH ), 45.2 (+, NCH ) ppm. IR (ATR): 3057, 3027, 1631, 1602,
(
(
+), 125.8 (+), 125.44 (+), 125.37 (+), 125.31 (+), 118.9 (+), 52.7 1583, 1523, 1497, 1443, 1380, 1356, 1334, 1230, 1174, 1141,
+), 44.8 (+) ppm. IR (ATR): 3055, 3023, 1600, 1524, 1442, 1378, 1115, 1073, 1024, 936, 830, 769, 744, 702, 619, 556, 524, 504,
1
249, 1222, 1178, 1157, 1138, 1058, 1008, 911, 852, 797, 766,
1
0 | Org. Biomol. Chem. 2018, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
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Page 11 of 12
O rP gl ea na si ce &d Bo i on mo to al e dc juu l sa tr mC ha er mg i ins ts ry
Journal Name
ARTICLE
38 2
H N
[M]2+ 333.1512, 1582, 1524, 1451, 1382, 1228, 1173, 1040, 952, 920, 827, 771,
-1
4
19 cm . HRMS (ESI): m/z calcd for C50
View Article Online
DOI: 10.1039/C9OB00357F
-1
found 333.1518.
753, 740, 614, 556, 494, 440, 413 cm .
1
3
-(1-Methylquinolinium-3-yl)-2-(1-methylquinolinium -4-yl)-
,4,5,6-tetraphenylbenzene dihexafluorophosphate (24b): A
solution of 0.050 g (0.079 mmol) of 1-(quinoline-3-yl)-2-
quinoline-4-yl)-3,4,5,6-tetraphenylbenzene 19b, 1 drop of
nitrobenzene and 0.02 mL (0.21 mmol) of dimethyl sulfate in 5
mL of anhydrous toluene was heated for 3 h under reflux
temperature, cooled to rt and extracted with water (3×5 mL)
(
1
2
F. J. Schmitz, K. H. Hollenbeak, D. C. Campbell, J. Org.
Chem., 1978, 43, 3916.
(a) N. Fusetani, N. Asai, S. Matsunaga, Tetrahedron Lett.,
1
994, 23, 3967. (b) H. Anan, N. Seki, O. Noshiro, K. Hona,
and then precipitated with excess of NH
PF
4 6
(1.3 equiv) to give
K. Yasumuro, T. Ozasa, N. Fusetani, Tetrahedron, 1996,
2, 10849.
5
1
3
0
-(1-methylquinolinium-3-yl)-2-(1-methylquinolinium-4-yl)-
3
S. Albrizio, P. Ciminiello, E. Fattorusso, S. Magno, J. R.
Pawlik, J. Nat. Prod., 1995, 58, 647.
,4,5,6-tetraphenylbenzene dihexafluorophosphate 24b. Yield
1
.067 g, 89%, a yellow solid, mp 245 °C (decomp.). H NMR (600
4
5
6
C. A. Volk, M. Köck, Org. Lett., 2003, 5, 3567.
C. A. Volk, M. Köck, Org. Biomol. Chem., 2004, 2, 1827.
R. Laville, O. P. Thomas, F. Berrue, F. Reyes, P. Amade,
Eur. J. Org. Chem., 2008, 121.
6
MHz, DMSO-d ), two sets of isochronous rotameric forms
(
24b*/24b# = 1 : 1.27) with close chemical shifts, exact
#
description of the coupling constants is not possible: 훿 = 9.54
#
7
(a) K. A. Smith, A. Streitwieser, Jr., J. Org. Chem., 1983,
(d, J = 1.3 Hz, 1H, 2-H), 9.23* (d, J = 1.5 Hz, 1H, 2-H), 9.20 (d, J
4
8, 2629. (b) K. C. Waterman, A. Streitwieser, Jr., J. Am.
=
1
8
7
7
4
6.3 Hz, 1H, 2ʹ-H), 9.18* (d, J = 6.4 Hz, 1H, 2ʹ-H), 9.02* (d, J =
Chem. Soc., 1984, 106, 3874. (c) K. A. Smith, K. C.
Waterman, A. Streitwieser, Jr., J. Org. Chem., 1985, 50,
3360. (d) K. C. Waterman, D. V. Speer, A. Streitwieser,
Jr., G. C. Look, K. O. Nguyen, J. G. Stack, J. Org. Chem.,
1988, 53, 583. (e) A. S. Koch, K. C. Waterman, K. Banks,
A. Streitwieser, J. Org. Chem., 1990, 55, 6166. (f) A. S.
Feng, D. V. Speer, S. G. DiMagno, M. S. Konings, A.
Streitwieser, J. Org. Chem., 1992, 57, 2902.
#
#
.5 Hz, 1H, 4-H), 8.81 (s, 1H, 4-H), 8.34 (dd, J = 1.1, 8.6 Hz, 1H),
#
.26-8.20 (m, 6H), 8.16 (d, J = 6.3 Hz, 1H, 3ʹ-H), 8.15-8.07 (m,
#
H), 8.04-8.01 (m, 2H), 7.92* (ddd, J = 1.2, 6.8, 8.1 Hz, 1H), 7.85-
#
#
#
.79 (m, 2H), 7.21-6.62* (m, 40H, Ph), 4.37 (s, 3H, NʹCH
3
),
#
.346 (s, 3H, NCH
3
), 4.343* (s, 3H, NʹCH
3
), 4.10* (s, 3H, NCH
): 훿 = 155.64*/# (o, C4ʹ),
3
)
1
3
ppm. C NMR (150 MHz, DMSO-d
1
6
/#
#
#
55.59* (o, C4ʹ), 149.53 (+, C2), 149.31* (+, C2), 148.47 (+,
8
9
1
A. S. Koch, A. S. Feng, T. A. Hopkins, A. Streitwieser, J.
Org. Chem., 1993, 58, 1409.
F. G. Pühlhofer and R. Weiss, Eur. J. Org. Chem., 2004,
#
C2ʹ), 148.42* (+, C2ʹ), 147.14* (+, C4), 146.81 (+, C4), 142.92
o), 142.90 (o), 142.89 (o), 142.84 (o), 141.63 (o), 141.49 (o),
(
1
002.
1
40.37 (o), 140.21 (o), 138.56 (o), 138.48 (o), 138.35 (o), 138.31
0
(a) R. Weiss, R. Roth, R. H. Lowack, H. Bremer, Angew.
Chem., 1990, 102, 1164; Angew. Chem., Int. Ed. Engl.,
1990, 29, 1132. (b) R. Weiss, B. Pomrehn, F. Hampel, W.
Bauer, Angew. Chem., 1995, 107, 1446; Angew. Chem.,
Int. Ed. Engl., 1995, 34, 1319. (c) R. Weiss, R. May, B.
Pomrehn, Angew. Chem., 1996, 108, 1319; Angew.
Chem., Int. Ed. Engl., 1996, 35, 1232. (d) R. Weiss, S. M.
Huber, F. G. Pühlhofer, Eur. J. Org. Chem., 2005, 3530.
(e) R. Weiss, S. M. Huber, F. W. Heinemann, P. Audebert,
F. G. Pühlhofer, Angew. Chem., 2006, 118, 8228; Angew.
Chem. Int. Ed., 2006, 45, 8059. (f) R. Weiss, F. G.
Pühlhofer, J. Am. Chem. Soc., 2007, 129, 547.
#
(o), 137.54 (o), 137.52 (o), 137.48 (o), 137.43 (o), 136.38 (o,
C8a), 136.10* (o, C8a), 135.96 (+), 135.88 (+), 135.46 (+), 135.38
#
(
+), 133.36* (o, C), 133.23 (o, C), 132.26 (o), 132.21 (o),
32.05 (o), 131.97 (o), 131.16 (+), 130.88 (+), 130.73 (+), 130.63
+), 130.61 (+), 130.58 (+), 130.55 (+), 130.51 (+), 130.42 (+),
30.30 (+), 130.26 (+), 130.23 (+), 130.22 (+), 129.71 (+), 129.63
+), 129.50 (+), 128.60 (+), 128.32 (+), 127.88 (o), 127.71 (o),
27.61 (+), 127.59 (+), 127.44 (+), 127.37 (+), 127.15 (+), 127.07
+), 127.03 (+), 126.98 (+), 126.93 (+), 126.85 (+), 126.79 (+),
26.64 (+), 126.30 (+), 126.26 (+), 126.24 (+), 125.24 (+), 124.78
+), 119.34 (+), 119.02 (+), 118.86 (+), 45.37 (+), 45.33 (+), 45.30
+), 44.67* (+, NCH ) ppm. IR (ATR): 3057, 1619, 1605, 1588,
529, 1498, 1443, 1234, 1175, 1115, 1073, 1025, 1001, 918,
1
(
1
(
1
(
1
(
(
1
1
1
2
(a) A. Schmidt, T. Mordhorst, M. Nieger, Synthesis, 2006,
3
987. (b) A. Schmidt, J. C. Namyslo, T. Mordhorst,
3
Tetrahedron, 2006, 62, 6893. (c) A. Schmidt, T.
Mordhorst, M. Nieger, Tetrahedron, 2006, 62, 1667. (d)
A. Schmidt, T. Mordhorst, Synthesis, 2005, 781. (e) A.
Schmidt, J. Heterocyl. Chem., 2002, 39, 949.
1
-1
8
27, 765, 702, 619, 556, 492, 434 cm . HRMS (ESI): m/z calcd
2
+
38 2
for C50H N [M] 333.1512, found 333.1512.
(a) A. Schmidt, A. Hetzheim, Tetrahedron, 1997, 53,
Hexakis(1-methylquinolinium-3-yl)benzene
hexakis
1
295. (b) A. Schmidt, M. K. Kindermann, J. Org. Chem.,
hexafluorophosphate (25): According to Procedure 4, a
solution of 0.084 g (0.10 mmol) of hexakis(quinoline-3-
yl)benzene 21, 1 drop of nitrobenzene and 0.10 mL (1.00 mmol)
of dimethyl sulfate in 5 mL of anhydrous toluene was heated for
1998, 63, 4636. (c) A. Schmidt, M. Nieger, J. Chem. Soc.,
Perkin Trans. 1, 1999, 1325.
A. Schmidt, T. Mordhorst, Heterocycles, 2006, 68, 1393.
(a) A. Schmidt, T. Mordhorst, M. Nieger, Org. Biomol.
Chem., 2005, 3, 3788. (b) A. Schmidt, T. Mordhorst, T.
Habeck, Org. Lett., 2002, 4, 1375.
1
1
3
4
3
h under reflux temperature. Then the obtained salt was
dissolved in water and precipitated with 1.05 equiv of NH PF
4
6
15 (a) S. G. DiMagno, K. C. Waterman, D. V. Speer, A.
Streitwieser, J. Am. Chem. Soc., 1991, 113, 4679. (b) A.
S. Koch, A. S. Feng, T. A. Hopkins, A. Streitwieser, J. Org.
Chem., 1993, 58, 1409.
to give hexakis(1-methylquinolinium-3-yl)benzene hexakis-
hexafluorophosphate 25. Yield 0.171 g, 95%, a white solid, mp
1
1
95 °C (decomp.). H NMR (600 MHz, DMSO-d
6
): 훿 = 9.41-8.89
1
6
(a) K. Akiyama, S. Tero-Kubota, Y. Ikegami, J. Am. Chem.
Soc., 1983, 105, 3601. (b) Y. Ikegami, T. Muramatsu, K.
Hanaya, J. Am. Chem. Soc., 1989, 111, 5782. (c) K.
Okada, K. Matsumoto, M. Oda, H. Murai, K. Akiyama, Y.
Ikegami, Tetrahedron Lett., 1995, 36, 6689.
(
m, 12H), 8.34-8.16 (m, 18H), 8.00-7.92 (m, 6H), 4.44-4.28 (m,
1
1
1
8H) ppm. 13C NMR (150 MHz, DMSO-d
): 훿 = 148.7, 148.2,
6
37.9, 137.8, 137.7, 137.5, 137.0, 131.0, 130.4, 128.6, 128.0,
19.4, 45.97, 45.89, 45.85, 45.79 ppm. IR (ATR): 3084, 1631,
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 11
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O rP gl ea na si ce &d Bo i on mo to al e dc juu l sa tr mC ha er mg i ins ts ry
Page 12 of 12
ARTICLE
Journal Name
1
1
7
8
R. Weiss, R. May, B. Pohmrehn, Angew. Chem., 1996,
08, 1319; Angew. Chem., Int. Ed. Engl., 1996, 35, 1232.
(a) W. R. Boon, Chem. Ind. (London), 1965, 782. (b) A. L.
Black, L. A. Summers, J. Chem. Soc. C, 1969, 610. (c) E. C.
Campbell, E. E. Glover, G. Trenholm, J. Chem. Soc., 1969,
44 H. D. Katz, J. Org. Chem., 1987, 52, 3932. View Article Online
1
45 (a) A. Schmidt, S. Batsyts, A. Smeyanov, T. Freese, E. G.
DOI: 10.1039/C9OB00357F
Hübner, M. Nieger, J. Org. Chem., 2016, 81, 4202. (b) S.
Batsyts, F. J. Ramírez, J. Casado, J. C. Namyslo, A.
Schmidt, Z. Naturforsch., 2018, 73, 481. (c) A. Dreger, R.
Cisneros Camuña, N. Münster, T. A. Rokob, I. Pápai, A.
Schmidt, Eur. J. Org. Chem., 2010, 4296. (d) M. Liu, M.
Nieger, E. Hübner, A. Schmidt, Chem. Eur. J., 2016, 22,
5416.
1
987. (d) A. D. Dodge, Endeavour, 1970, 111, 130.
(a) C. N. Corder, J. L. Way, J. Med. Chem., 1966, 9, 638.
b) Y. Ashani, S. Cohen, J. Med. Chem., 1971, 14, 621. (c)
C. F. Barfknecht, F. W. Benz, J. P. Long, J. Med. Chem.,
1
2
9
0
(
1
971, 14, 1003.
46 S. Batsyts, R. Vedmid, J. C. Namyslo, M. Nieger, A.
Schmidt, Eur. J. Org. Chem., 2019, 1301.
47 M. S. El-Shall, K. P. C. Vollhardt, J. Mol. Struct.
(Theochem), 1989, 183, 175.
M. Komloova, K. Musilek, A. Horova, O. Holas, V. Dohnal,
F. Gunn-Moore, K. Kuca, Bioorg. Med. Chem. Lett., 2011,
2
1, 2505.
2
2
1
2
J. Hiller, M. Liu, A. Schmidt, Heterocycles, 2017, 94, 821.
M. Drev, U. Grošelj, B. Ledinek, F. Perdih, J. Svete, B.
Štefane, F. Požgan, Org. Lett., 2018, 20, 5268.
L. E. Harrington, J. F. Britten, K. Nikitin, M. J. McGlinchey,
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