Synthesis, spectroscopy and computational studies of some novel π-conjugated vinyl N-alkylated quinolinium salts and their precursor's

Article abstract of DOI:10.1016/j.molstruc.2015.11.011

A series of π-conjugated vinyl N-methylated quinolinium salts (3) and their precursor's N-alkylated quinolinium salts (2) were prepared and characterized by NMR, IR, UV-Vis and MS spectroscopy. It was confirmed that the hydroxyl and amino derivatives of vinyl N-methylated quinolinium salts lead to spiro type compounds (4). The syntheses of N-alkylated quinolinium salts were successful, and even multigram scale was achievable. The structures of 1,2-dimethylquinolinium iodide (2a) and 1-ethyl-2-methylquinolinium iodide (2b) were determined by single crystal X-ray diffraction method. NMR spectra showed readily diagnostic H-1 and C-13 signals from methyl and N-alkyl groups for both 2 and 3. The geometries of the studied compounds were optimized in singlet states using the density functional theory (DFT) method with B3LYP functional. In general, the predicted bond lengths and angles are in a good agreement with the values based on the X-ray crystal structure data.

Full text of DOI:10.1016/j.molstruc.2015.11.011

Journal of Molecular Structure 1106 (2016) 416e423
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: http://www.elsevier.com/locate/molstruc
Synthesis, spectroscopy and computational studies of some novel
p-
conjugated vinyl N-alkylated quinolinium salts and their precursor's
,
*
a
a
a
b
Jacek E. Nycz a , Karolina Czyz , Marcin Szala , Jan G. Malecki , George Shaw ,
_
Brendan Gilmore b, Marek Jon c
a Institute of Chemistry, University of Silesia, ul. Szkolna 9, PL-40007, Katowice, Poland
b School of Pharmacy, The Queens University of Belfast, Medical Biology Centre, 97 Lisburn Road, Belfast, BT9 7BL, UK
c Faculty of Chemistry, University of Wrocław, 14 Joliot-Curie Street, 50-383, Wrocław, Poland
a r t i c l e i n f o
a b s t r a c t
Article history:
A series of
p-conjugated vinyl N-methylated quinolinium salts (3) and their precursor's N-alkylated
Received 30 July 2015
Received in revised form
12 September 2015
Accepted 9 November 2015
Available online 14 November 2015
quinolinium salts (2) were prepared and characterized by NMR, IR, UVeVis and MS spectroscopy. It was
confirmed that the hydroxyl and amino derivatives of vinyl N-methylated quinolinium salts lead to spiro
type compounds (4). The syntheses of N-alkylated quinolinium salts were successful, and even multi-
gram scale was achievable. The structures of 1,2edimethylquinolinium iodide (2a) and 1-ethyl-2-
methylquinolinium iodide (2b) were determined by single crystal X-ray diffraction method. NMR
spectra showed readily diagnostic H-1 and C-13 signals from methyl and N-alkyl groups for both 2 and 3.
The geometries of the studied compounds were optimized in singlet states using the density functional
theory (DFT) method with B3LYP functional. In general, the predicted bond lengths and angles are in a
good agreement with the values based on the X-ray crystal structure data.
Keywords:
Quinoline
Vinyl quinolinium salt
Styryl quinolinium salt
Quinolinium salt
Spiro
© 2015 Elsevier B.V. All rights reserved.
Perkin condensation
Styryl dye
1. Introduction
used to stabilize reactive anionic species and used as anion sensors
[5,6]. Some of them such as 1,3edialkylimidazolium or
The quinolinium salts is a class of readily available compounds.
Similarly to other heteroarenium salts they possess nitrogen atom
with formal positive charge, where lone pair is connected with
proton, alkyl, aryl or other functional groups. The compounds have
increased water solubility due to their ionic form. Salts of cationic
alkaloids possessing pyridinium, quinolinium, and isoquinolinium
rings are widespread in nature, such as Berberine, Papaverinium
chloride, Thalifedine, Fissisaine or Fenfangjines D [1]. Quinolinium
1ealkylpyridinium compounds exhibited toxicity towards algae,
bacteria or fungi [7,8]. It was studied that pyridinium salts under-
went a unique cyclization reaction to produce bicyclicaziridines
with modest to high efficiency [9], and related isoquinolinium-3-
oxides or imines reacted in a similar manner [9]. The same pro-
cess was found to take place in complex and naturally occurring
systems, which was demonstrated by the transformation of ber-
berinephenolbetaines to cycloberberines [10]. This finding suggests
that the photoreaction of some heteroarylium salts have high
synthetic potential which could lead to interesting structurally and
stereochemically complex substances. Formal positive charge on
nitrogen atom makes pyridine ring in quinolinium salt constitution
more susceptible to nucleophiles attack, especially in 2 and/or 4
salts and related p-conjugated vinyl N-alkylated quinolinium salts
were used as DNA fluorescence sensor [2]. N-methylquinolinium
salts have been used as sensitive fluorescent indicators of many
anions, including biologically important intracellular chloride
anion [3]. The comparison of different anions suggests that the
quenching efficiency is related to the ease of anion oxidation. The
quenching mechanism possibly involves charge transfer from the
anion to the indicator [3,4]. The quinolinium salts have also been
positions [11]. This process involved a cation-
p interaction, which
played a crucial role in the recognition of ligands in biochemical
processes and in the formation of the tertiary structure of proteins
[12e14]. It also is one of the key forces for the construction of
various hosteguest complexes and supramolecules [15]. By
considering the present knowledge of quinolinium salts, it is
* Corresponding author.
E-mail address: jacek.nycz@us.edu.pl (J.E. Nycz).
http://dx.doi.org/10.1016/j.molstruc.2015.11.011
0022-2860/© 2015 Elsevier B.V. All rights reserved.

J.E. Nycz et al. / Journal of Molecular Structure 1106 (2016) 416e423
417
conceivable that further explorations on quinolinium salts and the
derivatives of vinyl N-alkylated quinolinium salts may lead to new
applications. Despite the potential value of vinyl N-alkylated qui-
nolinium salts, there are only limited examples of vinyl N-alkylated
quinolinium salts, often without NMR characteristics, to the best of
our knowledge according to literature data.
In a series of experiments we obtained five quinolinium salts
and eight vinyl N-methylated quinolinium salts. Additionally we
proved the tendency of the rearrangements of vinyl N-methylated
quinolinium salts to spiro type compounds, especially the ones
with hydroxyl and amino substituents on phenyl ring. This finding
could explain the lack of this type of compounds and their poor
biological activity. We reported some new approaches for the
synthesis of the aforementioned compounds with in-depth spec-
troscopic characterization. Additionally we carried out computa-
tional and X-ray studies to compare the atomic charges of selected
quinolinium salts, the energy of the frontier orbitals and the
conformation of groups, which have not been determined by
crystallographic studies yet.
[nm] (logε)): 320 (3.68), 240 (4.25), 220 (4.06), 204 (4.24); IR (KBr):
3059nArH; 2924nCH; 1602nC]C; 1579nC]N; X-ray CCDC 873830;
LCMS-IT-TOF [MꢁI]þ ¼ 172 (100%), HRMS (IT TOF): m/z Calcd for
C
12H14N-127þ [MeI]þ: 172.1126, Found 172.1120.
2-Methyl-1-(2-methylpropyl)quinolinium iodide (2c) (beige)
27.47 g (0.084 mol, 14%); m.p. ¼ 181.1 ꢀC; 1H NMR (DMSOed6;
400.2 MHz)
d
¼ 0.98 (bs, 6H, CH2CH(CH3)2), 2.29e2.41 (m, 1H,
CH2CH(CH3)2), 3.13 (s, 3H, CH3), 4.88 (bs, 2H, NCH2CH(CH3)2), 7.99
(t, J ¼ 7.5 Hz, 1H, aromatic), 8.14 (d, J ¼ 8.6 Hz, 1H, aromatic), 8.21
(ddd, J ¼ 8.9, 7.0, 1.5 Hz 1H, aromatic), 8.42 (dd, J ¼ 8.1, 1.4 Hz, 1H,
aromatic), 8.64 (d, J ¼ 9.1 Hz, 1H, aromatic), 9.13 (d, J ¼ 8.5 Hz, 1H,
aromatic); 13C{1H} NMR (DMSOed6; 125.78 MHz)
d
¼ 19.26, 23.30,
28.65, 56.91, 119.64, 125.66, 128.34, 129.11, 130.66, 134.98, 138.72,
145.85, 161.22; UVeVis (methanol; [nm] (logε)): 320 (3.54), 241
l
(4.12), 219 (4.04), 203 (4.22); IR (KBr): 3097nArH; 2957nCH; 1618nC]
C; 1598nC]N; LCMS-IT-TOF [MꢁI]þ ¼ 200 (100%), HRMS (IT TOF): m/
z Calcd for C14H18N-127þ [MeI]þ: 200.1439, Found 200.1433.
8eMethoxye1emethylquinolinium iodide (2d) (greenish)
9.03 g (0.030 mol, 5%); m.p. ¼ 129e130 ꢀC; 1H NMR (DMSO-d6;
400.2 MHz)
d
¼ 4.08 (s, 3H, OCH3), 4.79 (s, 3H, NCH3), 7.74 (dd,
2. Experimental
J ¼ 7.3,1.6 Hz,1H, aromatic), 7.92 (m, 2H, aromatic), 8.08 (dd, J ¼ 8.3,
5.8 Hz, 1H, aromatic), 9.14 (d, J ¼ 8.3 Hz, 1H, aromatic), 9.28 (d,
J ¼ 5.7 Hz, 1H, aromatic); 13C{1H} NMR (DMSO-d6; 100.6 MHz)
2.1. General
d
¼ 52.35, 57.78, 116.73, 122.45, 122.60, 130.79, 130.82, 132.10,
Commercially available chemicals and solvents were used
without further purification. The 1H and 13C NMR calculations were
performed with the ACD Labs NMR Predictor v.12 program
considering the influence of different solvents. 2-Methylquinolin-
8-ol (1a) was purchased from Aldrich, and quinolin-8-ol from
Maybridge and were crystallisated before used. The synthesis of 8-
methoxyquinoline (1b) followed our procedure described in the
literature [18] and for N-alkylated quinolinium salts 2a, 2b, 2c, 2d
and 2e [16,17,22,23].
147.48, 151.74, 152.18; UVeVis (methanol;
l [nm] (logε)): 461 (3.14),
257 (4.41), 222 (3.65), 204 (4.18); IR (KBr): 3097nArH; 2955nCH
;
2853nCH
;
1598nC]C
;
1536nC]N
;
1049nOeCH3
;
LCMS-IT-TOF
[MꢁI]þ ¼ 174 (100%), HRMS (IT TOF): m/z Calcd for C11H12NO-
127þ [MeI]þ: 174.0919, Found 174.0913.
2-methyl-1-(prop-2-en-1-yl)quinolinium
iodide
(2e)
(greenish) 145.55 g (0.468 mol, 78%); m.p. ¼ 160 ꢀC; 1H NMR
(DMSO-d6; 400.2 MHz)
d
¼ 3.07 (s, 3H, CH3), 4.98 (d, J ¼ 17.4 Hz, 1H,
CH), 5.34 (d, J ¼ 10.7 Hz, 1H, CH), 5.67 (m, 2H, NCH2), 6.20 (m, 1H,
CH), 7.99 (t, J ¼ 7.5 Hz,1H, aromatic), 8.21 (m, 2H, aromatic), 8.44 (d,
J ¼ 7.4 Hz, 1H, aromatic), 8.48 (d, J ¼ 9.0 Hz, 1H, aromatic), 9.18 (d,
J ¼ 8.5 Hz, 1H, aromatic); 13C{1H} NMR (DMSO-d6; 100.6 MHz)
2.2. Synthesis of N-alkylated quinolinium salts
Appropriate RI (R ¼ CH3, Et, CH2CH]CH2, Bui) (1.20 mol) was
added to the 1a or 1b (0.60 mol) at room temperature. After the
completion of addition, the reaction mixture was heated under
reflux for 16 h. The excess of RI was slowly evaporated at room
temperature. The crude product was purified by crystallization
from ethanol (or methanol) and dried over P4O10 to yield pre-
cipitates as follows:
d
¼ 22.39, 53.58, 118.49, 119.11, 125.49, 128.20, 129.10, 130.05,
130.52, 135.31, 138.60, 146.31, 161.15; UVeVis (methanol;
l [nm]
(logε)): 321 (3.52), 239 (4.08), 219 (3.89), 204 (4.12); IR (KBr):
3035nArH
;
2925nCH
;
1603nC]C
;
1525nC]N
;
LCMS-IT-TOF
[MꢁI]þ ¼ 184 (100%), HRMS (IT TOF): m/z Calcd for C13H14N-127þ
[MeI]þ: 184.1126, Found 184.1120.
1,2eDimethylquinolinium iodide (2a) (yellow) 128.25
g
2.3. Synthesis of vinyl N-methylated quinolinium salts. Method A
(0.450 mol, 75%); m.p. ¼ 184e185 ꢀC; 1H NMR (DMSOed6;
400.2 MHz)
d
¼ 3.11 (s, 3H, CH3), 4.47 (s, 3H, NCH3), 7.99 (t,
2a (10.0 g, 35.1 mmol) was partially dissolved in Ac2O (100 mL,
108 g, 1.06 mol), followed by the addition of appropriate benzal-
dehyde (50 mmol). The reaction was heated under reflux for 16 h,
and was filtered after completion. The solvent was evaporated from
the resulting solution. The crude product was purified by crystal-
lization from ethanol (or methanol) and dried over P4O10 to yield
precipitates as follows:
J ¼ 7.3 Hz,1H, aromatic), 8.15 (d, J ¼ 8.6 Hz,1H, aromatic), 8.24 (ddd,
J ¼ 8.9, 7.0 Hz, JHH ¼ 1.5 Hz 1H, aromatic), 8.42 (dd, J ¼ 8.1,1.2 Hz,1H,
aromatic), 8.61 (d, J ¼ 9.0 Hz, 1H, aromatic), 9.13 (d, J ¼ 8.6 Hz, 1H,
aromatic); 13C{1H} NMR (DMSOed6; 100.6 MHz)
d
¼ 23.09, 39.73,
118.89, 125.02, 127.65, 128.86, 130.17, 134.92, 139.06, 145.26, 161.02;
lit. [22]; UVeVis (methanol; [nm] (logε)): 320 (3.68), 239 (4.23),
220 (4.05), 204 (4.24); IR (KBr): 3045nArH; 2986nCH; 2916nCH
l
;
2-[(E)-2-(2-chlorophenyl)vinyl]-1-methylquinolinium iodide
1604nC]C
;
1582nC]N
;
X-ray CCDC 795822; LCMS-IT-TOF
(3a) (black) 1.856 g (4.56 mmol, 13%); m.p. ¼ 246 ꢀC; 1H NMR
[MeI]þ ¼ 158 (100%), HRMS (IT TOF): m/z Calcd for C11H12N-127þ
(DMSO-d6; 400.2 MHz)
d
¼ 4.60 (s, 3H, NCH3), 7.55 (m, 2H, aro-
[MeI]þ: 158.09697 Found 158.0964.
matic), 7.64 (m, 1H, aromatic), 8.01 (t, J ¼ 7.5 Hz, 1H, aromatic), 8.02
(d, J ¼ 15.5 Hz, 1H, vinyl), 8.16 (d, J ¼ 15.9 Hz, 1H, vinyl), 8.25 (m, 2H,
aromatic), 8.43 (dd, J ¼ 8.1, 1.3 Hz, 1H, aromatic), 8.59 (d, J ¼ 8.8 Hz,
1H, aromatic), 8.61 (d, J ¼ 9.0 Hz, 1H, aromatic), 9.16 (d, J ¼ 8.8 Hz,
1-Ethyl-2emethylquinolinium iodide (2b) (yellow) 127.37 g
(0.426 mol, 71%); m.p. ¼ 224e225 ꢀC; 1H NMR (DMSOed6;
400.2 MHz)
d
¼ 1.56 (t, J ¼ 7.3 Hz, 3H, CH3), 3.14 (s, 3H, CH3), 5.02 (q,
JHH ¼ 7.3 Hz, 2H, NCH2), 8.01 (t, J ¼ 7.5 Hz, 1H, aromatic), 8.15 (d,
J ¼ 8.6 Hz, 1H, aromatic), 8.25 (ddd, J ¼ 8.8, 7.1, 1.5 Hz 1H, aromatic),
8.44 (dd, J ¼ 8.1, 1.2 Hz, 1H, aromatic), 8.64 (d, J ¼ 9.0 Hz, 1H, aro-
matic), 9.13 (d, J ¼ 8.5 Hz, 1H, aromatic); 13C{1H} NMR (DMSOed6;
1H, aromatic); 13C{1H} NMR (DMSO-d6; 125.78 MHz)
d
¼ 40.45,
119.42, 121.88, 123.05, 127.86, 128.24, 129.05, 129.35, 130.15, 130.20,
132.47,132.56,134.08,135.30,139.21,140.61,145.19,155.64; UVeVis
(methanol;
l [nm] (logε)): 354 (3.92), 292 (3.68), 244 (4.05), 218
100.6 MHz)
d
¼ 13.35, 22.33, 47.12, 118.76, 125.45, 128.13, 128.90,
(4.24), 204 (4.39); IR (KBr): 3063nArH; 2960nCH; 1608nC]C; 1585nC]
130.51, 135.16, 137.93, 145.48, 160.40; lit. [23]; UVeVis (methanol;
l
N; LCMS-IT-TOF [MꢁI]þ ¼ 280 (100%), HRMS (IT TOF): m/z Calcd for

418
J.E. Nycz et al. / Journal of Molecular Structure 1106 (2016) 416e423
C18H15NCl-127þ [MeI]þ: 280.0893, Found 280.0887.
152.84, 156.31; lit. [24]; UVeVis (methanol;
l [nm] (logε)): 526
2-[(E)-2-(4-chlorophenyl)vinyl]-1-methylquinolinium iodide
(4.44), 328 (3.73), 280 (3.63), 222 (4.16), 204 (4.26); IR (KBr):
(3b) (black) 1.856 g (4.56 mmol, 13%); m.p. ¼ 171 ꢀC; 1H NMR
3046nArH
;
2906nCH
;
1565nCH
;
1529nC]C
;
LCMS-IT-TOF
(DMSO-d6; 400.2 MHz)
d
¼ 4.59 (s, 3H, NCH3), 7.64 (d, J ¼ 8.4 Hz,
[MꢁI]þ ¼ 289 (100%), HRMS (IT TOF): m/z Calcd for C20H21N2-
2H, aromatic), 8.00 (m, 4H aromatic), 8.19 (d, J ¼ 16.2 Hz, 1H, vinyl),
8.22 (m, 1H, vinyl), 8.39 (d, J ¼ 7.9 Hz, 1H, aromatic), 8.57 (d,
J ¼ 8.7 Hz, 1H, aromatic), 8.59 (d, J ¼ 8.7 Hz, 1H, aromatic), 9.13 (d,
J ¼ 8.9 Hz, 1H, aromatic); 13C{1H} NMR (DMSO-d6; 125.78 MHz)
127þ [MeI]þ: 289.1705, Found 289.1699.
2.4. Synthesis of vinyl N-methylated quinolinium salts. Method B
d
¼ 40.13, 119.39, 120.25, 121.24, 127.98, 129.19, 129.21, 130.12,
The synthesis of vinyl N-alkylated quinolinium salts 3g and 3h
followed our procedure described in the literature [19e21]: 2a
(10.0 g, 35.1 mmol) was partially dissolved in Ac2O (100 mL, 108 g,
1.06 mol), followed by the addition of appropriate benzaldehyde
(50 mmol). The reaction was heated under reflux for 16 h. Then the
solvent was evaporated from the resulting solution. A pyridine/H2O
system (v/v 4:1; 50 mL) was added and the reaction mixture was
stirred under further reflux for 16 h. The crude product was purified
by crystallization from ethanol (or methanol) and dried over P4O10
to yield precipitates as follows:
130.76, 133.75, 135.07, 135.89, 139.21, 144.48, 145.19, 155.94;
UVeVis (methanol; [nm] (logε)): 377 (3.87), 300 (3.63), 247
l
(3.90), 211 (4.17), 204 (4.19); IR (KBr): 3060nArH; 3012nCH; 1603nC]
C; 1571nC]N; LCMS-IT-TOF [MꢁI]þ ¼ 280 (100%); HRMS (IT TOF):
m/z Calcd for C18H15NCl-35þ [MeI]þ: 280.0893, Found 280.0891.
2-[(E)-2-(4-bromophenyl)vinyl]-1-methylquinolinium
io-
dide (3c) (black) 8.865 g (19.66 mmol, 56%); m.p. ¼ 227.6 ꢀC; 1H
NMR (DMSO-d6; 400.2 MHz)
d
¼ 4.59 (s, 3H, NCH3), 7.77 (d,
J ¼ 8.4 Hz, 2H, aromatic), 7.92e8.01 (m, 3H, aromatic), 8.00 (d,
J ¼ 16.0 Hz, 1H, vinyl), 8.18 (d, J ¼ 15.9 Hz, 1H, vinyl), 8.23 (d,
J ¼ 7.5 Hz, 1H, aromatic), 8.39 (d, J ¼ 8.0 Hz, 1H, aromatic), 8.58 (d,
J ¼ 8.8 Hz, 1H, aromatic), 8.59 (d, J ¼ 8.8 Hz, 1H, aromatic), 9.13 (d,
J ¼ 8.9 Hz, 1H, aromatic); 13C{1H} NMR (DMSO-d6; 125.78 MHz)
2-[(E)-2-(2-Hydroxyphenyl)ethenyl]-1-methylquinolinium
iodide (3g) (brick red) 1.229 g (3.16 mmol, 9%); m.p.dec. ¼ 228.9 ꢀC;
1H NMR (DMSO-d6; 500.18 MHz)
d
¼ 4.53 (s, 3H, NCH3), 6.97 (t,
J ¼ 7.5 Hz, 1H, aromatic), 7.01 (dd, J ¼ 8.2, 0.8 Hz, 1H, aromatic), 7.36
(td, J ¼ 8.1, 1.6 Hz, 1H, aromatic), 7.92 (dd, J ¼ 7.9, 1.5 Hz, 1H, aro-
matic), 7.95 (m, 1H, aromatic), 7.97 (d, J ¼ 16.3 Hz, 1H, vinyl), 8.18
(ddd, J ¼ 8.8, 7.1, 1.5 Hz,1H, aromatic), 8.24 (d, J ¼ 16.0 Hz,1H, vinyl),
8.37 (dd, J ¼ 8.1, 1.3 Hz, 1H, aromatic), 8.54 (d, J ¼ 8.9 Hz, 1H, aro-
matic), 8.55 (d, J ¼ 8.8 Hz, 1H, aromatic), 9.03 (d, J ¼ 8.9 Hz, 1H,
aromatic), 10.65 (s, 1H, OH); 13C{1H} NMR (DMSO-d6; 125.78 MHz)
d
¼ 41.18, 119.43, 120.34, 121.28, 124.89, 128.00, 129.20, 130.12,
131.81, 131.72, 134.11, 135.08, 139.23, 144.48, 145.29, 155.97; UVeVis
(methanol; [nm] (logε)): 378 (4.24), 301 (3.88), 247 (4.10), 209
l
(4.39), 204 (4.40); IR (KBr): 3050nArH; 3023nCH; 1607nC]C; 1574nC]
N; LCMS-IT-TOF [MꢁI]þ ¼ 324 (100%), HRMS (IT TOF): m/z Calcd for
C
18H15NBr-127þ [MeI]þ: 324.0388, Found 324.0382.
2-[(E)-2-(4-methoxyphenyl)ethenyl]-1-methylquinolinium
d
¼ 39.82, 116.47, 118.85, 119.25, 119.68, 121.14, 121.67, 127.69,
128.87, 129.83, 130.09, 133.02, 134.86, 139.16, 142.47, 144.10, 156.67,
157.52; UVeVis (methanol; [nm] (logε)): 410 (4.09), 299 (3.78),
iodide (3d) (purple) 4.385 g (10.88 mmol, 31%); m.p. ¼ 230.5 ꢀC; 1H
NMR (DMSO-d6; 400.2 MHz)
d
¼ 3.86 (s, 3H, NCH3), 4.54 (s, 3H,
l
CH3), 7.11 (d, J ¼ 8.7 Hz, 2H, aromatic), 7.79 (d, J ¼ 15.8 Hz,1H, vinyl),
7.90e8.00 (m, 3H, aromatic), 8.17 (dt, J ¼ 7.4, 1.2 Hz, 1H, aromatic),
8.22 (d, J ¼ 15.8 Hz, 1H, vinyl), 8.34 (d, J ¼ 7.3 Hz, 1H, aromatic), 8.55
(t, J ¼ 8.8 Hz, 2H, aromatic), 9.01 (d, J ¼ 9.0 Hz, 1H, aromatic); 13C
248 (3.74), 216 (4.20), 204 (4.17); IR (KBr): 3163nArH; 3005nCH;
1597nCH; 1572nC]C; LCMS-IT-TOF [MꢁI]þ ¼ 262 (100%), HRMS (IT
TOF): m/z Calcd for C18H16NO-127þ [MeI]þ: 262.1232, Found
262.1264.
{1H} NMR (DMSO-d6; 125.78 MHz)
d
¼ 39.78, 55.63, 114.74, 116.58,
2-[(E)-2-(4-Hydroxyphenyl)ethenyl]-1-methylquinolinium
119.29, 120.83, 127.57, 127.66, 128.82, 130.04, 131.42, 134.75, 139.20,
143.64, 147.18, 156.38, 162.19; lit. [24]; UVeVis (methanol; [nm]
(logε)): 415 (4.10), 288 (3.77), 257 (3.88), 216 (4.20), 203 (4.18); IR
iodide (3h) (brick red) 5.598
g
(14.39 mmol, 41%);
l
m.p.dec. ¼ 254.4 ꢀC; 1H NMR (DMSO-d6; 400.2 MHz)
¼ 4.52 (s, 3H,
d
NCH3), 6.92 (d, J ¼ 8.5 Hz, 2H, aromatic), 7.71 (d, J ¼ 15.8 Hz, 1H,
vinyl), 7.90 (m, 3H, aromatic), 8.15 (t, J ¼ 7.9 Hz, 1H, aromatic), 8.21
(d, J ¼ 15.7 Hz, 1H, vinyl), 8.32 (d, J ¼ 7.8 Hz, 1H, aromatic), 8.52 (d,
J ¼ 9.0 Hz, 1H, aromatic), 8.56 (d, J ¼ 9.1 Hz, 1H, aromatic), 8.98 (d,
J ¼ 9.0 Hz, 1H, aromatic), 10.38 (s, 1H, OH); 13C{1H} NMR (DMSO-d6;
(KBr): 3068nArH
;
2955nCH
;
2832nCH
;
1745nC]C
;
1588nC]N;
1173nOeCH3; LCMS-IT-TOF [MꢁI]þ ¼ 276 (100%), HRMS (IT TOF): m/
z Calcd for C19H18NO-127þ [MeI]þ: 276.1388, Found 276.1382.
1-methyl-2-[(E)-2-(4-nitrophenyl)ethenyl]quinolinium io-
dide (3e) 11.444 g (27.38 mmol, 78%); m.p. ¼ 243.5 ꢀC; 1H NMR
125.78 MHz)
d
¼ 40.18, 115.34, 116.08, 119.14, 120.69, 126.19, 127.35,
(DMSO-d6; 400.2 MHz)
d
¼ 4.64 (s, 3H, NCH3), 8.02 (t, J ¼ 7.5 Hz, 1H,
128.59, 129.92, 131.73, 134.57, 139.12, 143.26, 147.72, 156.41, 161.16;
UVeVis (methanol; [nm] (logε)): 424 (4.28), 398 (3.64), 260
aromatic), 8.18 (d, J ¼ 16.1 Hz, 1H, vinyl), 8.26 (m, 4H, 3H aromatic
and 1H vinyl), 8.38 (d, J ¼ 8.7 Hz, 2H, aromatic), 8.42 (d, J ¼ 8.0 Hz,
1H, aromatic), 8.62 (t, J ¼ 8.6 Hz, 2H, aromatic), 9.20 (d, J ¼ 8.8 Hz,
l
(3.88), 217 (4.25), 203 (4.16); IR (KBr): 3421nOH; 3056nArH; 2810nCH
;
1575nCH; 1521nC]C; LCMS-IT-TOF [MꢁI]þ ¼ 262 (100%), HRMS (IT
TOF): m/z Calcd for C18H16NO-127þ [MeI]þ: 262.1232, Found
262.1264.
1H, aromatic); 13C{1H} NMR (DMSO-d6; 125.78 MHz)
d
¼ 40.48,
119.53, 121.62, 123.77, 124.17, 128.33, 129.49, 130.01, 130.19, 135.35,
139.27, 140.98, 143.45, 145.03, 148.33, 155.50; UVeVis (methanol;
[nm] (logε)): 368 (4.18), 298 (3.89), 253 (3.70), 217 (4.12), 204
l
2.5. Synthesis of (2S,R)-1-methyl-1H,10H-2,20-spirobi[quinoline] (4)
(4.21); IR (KBr): 3065nArH; 2999nCH; 1599nCH; 1573nC]C; 1613nNO2
;
1440nNO2; LCMS-IT-TOF [MꢁI]þ ¼ 291 (100%), HRMS (IT TOF): m/z
Calcd for C18H15N2O2-127þ [MeI]þ: 291.1134, Found 291.1128.
2-{(E)-2-[4-(dimethylamino)phenyl]ethenyl}-1-
2-Aminobenzaldehyde (6.05 g, 50 mmol) was dissolved in Ac2O
(100 mL, 108 g, 1.06 mol). Subsequently, 2a (10.0 g, 35.1 mmol) was
added, and the reagents were heated under reflux for 16 h. After
solvent removal by evaporating from the resulting solution, ethanol
was added and the reaction mixture was stirred under reflux for
16 h, followed by filtration. To the solution H2SO4 (ca. 10%) was
added, and the reaction mixture was stirred under reflux for 4 h.
After stirring, chloroform (200 mL) was added and the resulting
two-layer system was carefully brought to a neutral pH by adding
aqueous KOH solution (ca. 10%). The organic layer was separated
and the aqueous layer was extracted four times with chloroform.
The combined organic layers were dried over MgSO4. After solvent
methylquinolinium iodide (3f) 12.119 g (29.13 mmol, 83%);
m.p. ¼ 268 ꢀC; 1H NMR (DMSO-d6; 400.2 MHz)
d
¼ 3.07 (s, 6H,
2CH3), 4.44 (s, 3H, NCH3), 6.81 (d, J ¼ 8.8 Hz, 2H, aromatic), 7.54 (d,
J ¼ 15.4 Hz, 1H, vinyl), 7.84 (m, 3H, aromatic, vinyl), 8.08 (t,
J ¼ 7.5 Hz, 1H, aromatic), 8.23 (s, 1H, aromatic), 8.25 (d, J ¼ 9.5 Hz,
1H, aromatic), 8.42 (d, J ¼ 8.9 Hz, 1H, aromatic), 8.50 (d, J ¼ 9.2 Hz,
1H, aromatic), 8.80 (d, J ¼ 9.1 Hz, 1H, aromatic); 13C{1H} NMR
(DMSO-d6; 125.78 MHz)
122.38, 126.77, 127.98, 129.76, 131.96, 134.10, 139.18, 141.85, 148.89,
d
¼ 38.98, 39.68, 111.82, 118.80, 120.18,

J.E. Nycz et al. / Journal of Molecular Structure 1106 (2016) 416e423
419
evaporating, the crude product was purified by crystallization from
the mixture of CHCl3 and hexane.
y,1-z and 1-x,1-y,1-z in 2b. The centroidecentroid distances vary
from 3.80 Å and 3.94 Å (phenyl rings) to 3.50 Å and 3.54 Å (pyridine
rings) and the shift distances are in the range 1.98, 1.42 Å to 1.00,
0.94 Å in 2a and 2b, respectively. Our observations are consistent
with A. N. Swinburne et al. work [5].
2.6. Crystallography
Data for compound 2a was collected on a KUMA KM4 diffrac-
2.7. Instrumentation
tometer with graphiteemonochromated Mo K
a radiation using
Sapphiree2 CCD detector. The apparatus was equipped with an
open flow thermostat (Oxford Cryosystems) with enabled experi-
ments at 120 K. The stream of nitrogen also prevented the spec-
imen from contact with moisture and oxygen. The structures were
solved by direct methods and refined by fullematrix leastesquares
on F2 (all data) using the SHELXTL program package [25,26]. All
nonehydrogen atoms were refined anisotropically. Hydrogen
atoms were refined in geometrically idealised positions with
isotropic temperature factors 1.2 times the equivalent isotropic
temperature factor Ueq of their attached atoms (1.5 for CH3
groups). For compounds 2b the X-ray measurements were per-
formed with Oxford Diffraction Gemini A Ultra diffractometer with
NMR spectra were obtained with Bruker Avance 400 operating
at 400.13 MHz (1H) and 100.4 MHz (13C) at 30 ꢀC; chemical shifts
referenced to ext. TMS (1H, 13C); positive signs of chemical shifts
denote shifts to lower frequencies, coupling constants are given as
absolute values. Melting points are uncorrected.
3. Results and discussion
The synthesis of N-alkylated quinolinium salts (2) based on the
reaction of 1a and 1b with appropriate RI (R ¼ CH3, Et, CH2CHCH2,
Bui) were carried out under reflux with a set of identical reaction
conditions (Scheme 1) according to already published methodology
[16,17,22,23]. Reactions were successful even in multigram scale
with isolated yields up to 78%, except 2d (5%). The pattern of the
yield distribution depends on the substituent location on the pyr-
idinium ring through steric and/or electronic effect. The reaction
presented on Scheme 1 showed that the impact on the nitrogen
atom reactivity is not only from methyl group on C2, but also from
methoxy group on peri position (C8) for 2d.
The synthesis of 3 was based on the reactions of 2a with
appropriate benzaldehyde, which were carried out under reflux
with a set of identical reaction conditions (Scheme 2). The pattern
of the yield distribution depends on isolation procedure. Com-
pounds with low solubility were easily precipitated giving higher
isolation yield up to 83% for 3f. Two protocols for the synthesis of 3
were elaborated. Firstly method A was designed for compounds
possessing non-nucleophilic substituents, such as halogens or
nitro. Secondly, method B was dedicated for molecules with
nucleophilic substituents such as hydroxyl or amino functional
groups based on already published methodology [19e21].
graphiteemonochromated Mo K
crystal was measured at room temperature (295 K). During the data
collection scans were performed and absorption corrections were
a
radiation (
l
¼ 0.71073 Ǻ). The
u
used. The structure was solved and refined with the use of SHELX
software [23]. All nonehydrogen atoms were refined with aniso-
tropic temperature factors. All H atoms bound to C atoms were
refined using a riding model with CeH distances of 0.95 Å or 0.98 Å
and Uiso(H) values of 1.2Ueq(C), or 1.5 Ueq(C), respectively. H
atoms, which take part in hydrogen bonds, were allowed to ride at
the positions deduced from the difference maps with Uiso(H) equal
to 1.2Ueq(C), 1.2Ueq(N) or 1.5Ueq(O). 2a and 2b crystallize in
monoclinic P21/n and P21/c space groups. The molecular structures
of the compounds are shown in Fig. 1.
The crystal data and structure refinement details are presented
in Table 1. The selected distances and angles of the 2a and 2b
compounds are collected in Table 1, and it can be seen that the
values are normal.
Except the hydrogen bond linking the iodine anion and proton
in position
4 in pyridine ring C(3)eH(3)/I(1) [-x ,-y, 1-z]
(H/A ¼ 2.98 Å, D/A ¼ 3.884(3) Å and DdH/A angle 165.0ꢀ) in
From the theoretical point of view, positive charges for both
carbons atoms C2 and C4 (ortho and para positions) should be
expected, which is correct for 2b (0.664 and 0.199, respectively).
However, for 2a only C2 has positive charge (0.371), C4 has negative
charge, close to zero (ꢁ0.093) (Fig. 3). The atomic charge calcula-
tions for 2a and 2b showed that methylated nitrogen atom had
the crystal structures, 2a and 2b form the p-stacking interactions as
one can see in Fig. 2.
There are interactions between the phenyl C(4)eC(9) and pyri-
dine N(1)eC(1)eC(9) rings in the molecules, which are generated
by 1ex, -y, 1-z and -x; -y; 1-z symmetry operations in 2a and ex, 1-
Fig. 1. ORTEP drawing of 2a (right) and 2b (left) with 30% probability displacement ellipsoids.

420
J.E. Nycz et al. / Journal of Molecular Structure 1106 (2016) 416e423
Table 1
Crystal data and structure refinement details of 2a and 2b compounds.
2a
2b
Empirical formula
Formula weight
C11H12N, I
285.12
C12H14N, I
299.14
Temperature [K]
120(2)
295(2)
Crystal system
Space group
Monoclinic
P21/n
Monoclinic
P21/c
Unit cell dimensions
a [Å]
6.8937(3)
7.1855(3)
b [Å]
c [Å]
10.1321(4)
15.9019(6)
96.871(4)
1102.74(8)
4
15.9261(5)
10.3344(4)
94.722(3)
1178.62(7)
4
b
V [Å3]
Z
Calculated density [Mg/m3]
1.717
1.686
MoeKa
l
[Å]
0.71073
2.860
552
0.71073
2.680
584
Absorption coefficient [mmꢁ1
F(000)
]
Crystal dimensions [mm]
q
0.12 ꢂ 0.09 ꢂ 0.05
3.38 to 25.05
ꢁ8 ꢃ h ꢃ 8
ꢁ12 ꢃ k ꢃ 12
ꢁ18 ꢃ l ꢃ 18
19,810
0.19 ꢂ 0.10 ꢂ 0.08
3.57 to 25.05
ꢁ8 ꢃ h ꢃ 8
ꢁ18 ꢃ k ꢃ 18
ꢁ12 ꢃ l ꢃ 12
6826
range for data collection [ꢀ]
Index ranges
Reflections collected
Independent reflections
Data/restraints/parameters
Goodness-of-fit on F2
1952 [R(int) ¼ 0.0288]
1952/0/120
1.073
2086 [R(int) ¼ 0.0264]
2086/0/129
1.049
Final R indices [I > 2
s
(I)]
R1 ¼ 0.0207
wR2 ¼ 0.0539
R1 ¼ 0.0252
wR2 ¼ 0.0546
0.313 and ꢁ0.561
795822
R1 ¼ 0.0234
wR2 ¼ 0.0491
R1 ¼ 0.0319
wR2 ¼ 0.0518
0.345 and ꢁ0.532
873830
R indices (all data)
Largest diff. Peak and hole [e Åꢁ3
CCDC number
]
Fig. 2. The
p
-stacking interactions in the structures of 2a (right) and 2b (left).
Scheme 2. Synthesis of 3. Reagents and conditions: (i); Ac2O, appropriate benzalde-
hyde, reflux (ii); PY, H2O, reflux.
impact on their chemical reactivity. The deprotonation of hydroxyl
or amino group located on ortho position on the phenyl ring of vinyl
N-methylated quinolinium salts 3g and 3h analogues could intro-
duce intramolecular cyclization led to spiro type compounds 4,
which was postulated by Zakhs et al. (Scheme 3) [30,31]. For hy-
droxyl or amino group located on para or meta position on phenyl
ring 3, a condensation reaction should lead to polymeric material.
Scheme 1. Synthesis of 2. Reagents and conditions: (i); R00I, reflux, 16 h.
positive charge (0.199) for 2b, and has negative charge (ꢁ0.472) for
2a.
The presence of positively charged carbon atom C2, which is
close to positive charged methylated nitrogen atom, could have an

J.E. Nycz et al. / Journal of Molecular Structure 1106 (2016) 416e423
421
Fig. 3. Natural atomic charges of 2a (left) and 2b (right).
1521 cmꢁ1 to 1598 cmꢁ1are assigned to the stretches of C]N and
C]C in quinoline ring (Table 3). In the case of 3d, the stretching
vibration of the C]C double bond on vinyl moiety gives band at
1745 cmꢁ1, and the shift is connected with methoxy group in para
position in the phenyl ring.
Scheme 3. Synthesis of (2S,R)-1-methyl-1H,10H-2,20-spirobi[quinoline] (4). Both 4a an
4b showed helical chirality.
3.3. DFT calculations and electronic spectra
The calculations were carried out by using Gaussian 09 [27]
program. The DFT/B3LYP [28] method was used for the geometry
optimization and electronic structure determination. The geometry
optimization was made for gas phase molecule in both cationic and
neutral forms. For each form a frequency calculation was carried
out, verifying that the optimized molecular structure obtained
corresponds to energy minimum, thus only positive frequencies
were expected. The calculations were performed using the polari-
The presence of racemic 4a and 4b were proved by NMR techniques
(see below).
3.1. NMR
The 1H NMR and 13C NMR solution spectra of 2 and 3 showed
distinctive H-1 and C-13 signals from C2eCH3 and N-CH3 functional
groups (Table S1, Supplementary data). The experimental 1H and
13C chemical shifts of aromatic carbons and protons of 2 in DMSO-
d6 possess almost the same values. The analysis of the trends in 1H
chemical shifts of vinyl functional group in 3 revealed that the
electron donating substituents such as methoxy (3d), dimethyla-
mino (3f) or hydroxyl (3g, 3h) on phenyl group in the constitution
of 3 significantly increased the shielding effect (upfield effect,
zation functions for all atoms: 6-31G**
hydrogen and Lanl2dz ECP [29] for iodine.
e carbon, nitrogen,
The geometry of 2a and 2b were optimized in singlet states
using the DFT method with the B3LYP functional. Some optimized
geometric parameters of the compounds are listed in Table 1.
Comparing the theoretical data with the experimental values in-
dicates that optimized bond lengths and angle values are slightly
different with the experimental results. It should be noted that the
geometry of the solid state structure is subject to intra and inter-
molecular interactions, such as hydrogen bonding and van der
Waals interactions. As seen in Table 2, the largest discrepancies
between the calculated and experimental geometrical parameters
are observed in N(1)eC(1) and C(1)eC(11) bonds. The largest dif-
ference between experimental and calculated DFT bond length is
0.03 Å which suggest that the calculation precision is satisfactory.
Similar situation is also observed for calculated bond angles with
DFT method. The good agreement between experimental IR spec-
trum and the calculated IR frequencies, as one can see on the Fig. 5,
also confirms the optimized geometry of the compound. Both
electronic structures of the compound were calculated for cationic
and neutral forms. Since the frontier HOMOs in the neutral forms of
the compounds are located on the p orbital of iodine anion (see
Fig. 6), the HOMO/LUMO transitions have charge transfer
characteristics.
smaller d), resulting in the decreased chemical shifts of selected H-1
signals in comparison with nitro group (3e). The analysis of the
value of coupling constants (ca. 16 Hz) for vinyl protons confirmed
the sole presence of E conformer (Table S2, Supplementary data).
For signal assignments, heteronuclear 2D 1He13C spectra hetero-
nuclear multiple quantum correlation (HMQC) and heteronuclear
single quantum correlation (HSQC) were used. The analysis of the
1H NMR and 13C NMR spectra in basic solvents such as KOD/D2O/
DMSO-d6 by comparing with neutral DMSO-d6 revealed that the
hydroxyl derivatives and their amino analogues of vinyl N-meth-
ylated quinolinium salts 3g and 3h could form spiro type structure
through intramolecular and intermolecular condensation reaction
(Scheme 3). The coupling constants (ca. 3 Hz only from crude re-
action mixture) of vinyl protons indicated presence of Z conformer,
the spiro type compounds 4. For signal assignments, heteronuclear
2D 1He13C spectra heteronuclear multiple quantum correlation
(HMQC) and heteronuclear single quantum correlation (HSQC)
were used (Fig. 4).
The first, lowest energy, bands on the UVeVis spectra of 2a, 2b
and 2c are in the UV region (320 nm); in the case of the vinyl
compounds the maxima are shifted to lower energy due to the
extended conjugated double bonds system. Moreover the UVeVis
spectra of the 3d, 3g, 3h as well as 2d compounds present maxima
on the visible region (above 400 nm) what is associated with the
presence of electron donating substituents, as methoxy or hydroxyl
groups, in the molecules of these compounds. The comparison
3.2. IR
The IR spectra of the compounds are similar, and Fig. 5 presents
the spectrum of 2a as example. The characteristically sharp and
strong bands with maxima close to 1600 cmꢁ1 and in the range

422
J.E. Nycz et al. / Journal of Molecular Structure 1106 (2016) 416e423
Fig. 4. HMQC spectrum of 4, vinyl region.
Table 2
Selected bond lengths and angles for 2a and 2b (Å and ꢀ).
2a
2b
exp
calc
exp
calc
Bond lengths [Å]
N(1)dC(1)
N(1)dC(9)
N(1)dC(10)
C(1)eC(2)
C(1)eC(11)
C(4)dC(9)
C(4)dC(3)
C(4)dC(5)
1.335(3)
1.394(3)
1.475(3)
1.402(4)
1.484(4)
1.405(4)
1.406(4)
1.417(4)
1.387(4)
1.396(4)
1.361
1.402
1.469
1.424
1.509
1.422
1.424
1.412
1.404
1.409
1.341(3)
1.396(3)
1.494(3)
1.398(4)
1.486(4)
1.414(4)
1.399(4)
1.417(4)
1.400(5)
1.402(4)
1.516(4)
1.355
1.400
1.496
1.408
1.505
1.429
1.412
1.420
1.413
1.414
1.530
C(6)dC(7)
C(8)dC(9)
C(10)dC(12)
Bond angles [ꢀ]
C(1)dN(1)dC(9)
C(1)dN(1)dC(10)
C(9)dN(1)dC(10)
N(1)dC(1)dC(11)
N(1)dC(10)dC(12)
122.0(2)
120.5(2)
117.6(2)
121.1(3)
121.4
119.5
117.9
120.3
121.9(2)
119.9(2)
118.2(2)
121.0(3)
110.7(2)
121.8
119.5
118.7
120.8
112.7
Fig. 5. The experimental and calculated IR spectra of 2a.
between the spectra of 3a and 3b as well as 3g and 3h compounds
shows the difference between substituents located on ortho and
para position in benzene ring. The substituents in para-position
exert higher impact on electronic structure than one in 2 posi-
tions in the ring. The chloride in position 4 exerts more donating
impact than ortho substituent. The replacement of chloride for 3b
into bromide for 3c does not change the maximum of the lowest
energy band whereas increases the intensity of the band. The en-
ergies of HOMOs, LUMOs and electronic gaps for cationic quinolone
moieties present Fig. 7.
Table 3
Selected vibrational frequencies of studied 2 and 3.
nOH
nArH
nCH
nC]C
;
nC]N
nOeCH3
nNO2
2a
2b
2c
2d
2e
3a
3b
3c
3d
3e
3f
3045
3059
3097
3097
3035
3063
3060
3050
3068
3065
3046
3163
3056
2986; 2916
2924
2957
2955, 2853
2925
2960
3012
3023
2955; 2832
2999
2906
1604; 1582
1602; 1579
1618; 1598
1598; 1536
1603; 1525
1608; 1585
1603; 1571
1607; 1574
1745; 1588
1599; 1573
1565; 1529
1597; 1572
1575; 1521
1049
1173
4. Conclusion
1613; 1440
In the present studies, we reported the synthesis and spectro-
3g
3h
3005
2810
3421
scopic characterization of selected crystalline
p-conjugated vinyl
N-alkylated quinolinium salts (2) and their precursor's N-alkylated
quinolinium salts (3) using IR, UVeVis and multinuclear NMR
spectroscopic techniques. Both of 2a and 2b have been character-
ized by single crystal X-ray diffraction method. X-ray crystal
structure analysis of 2a and 2b showed the presence of the
p-
stacking interactions. The 1H and 13C NMR spectra of presented

J.E. Nycz et al. / Journal of Molecular Structure 1106 (2016) 416e423
423
dx.doi.org/10.1016/j.molstruc.2015.11.011.
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Acknowledgments
The GAUSSIAN09 calculations were carried out in the Wrocław
Centre for Networking and Supercomputing, WCSS, Wrocław,
Poland (http://www.wcss.wroc.pl grant number 18).
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Appendix A. Supplementary data
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Supplementary data related to this article can be found at http://
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