Synthesis and spectroscopic characterisation of N-alkyl quaternary ammonium salts typical precursors of cyanines

Article abstract of DOI:10.3390/70300320

The synthesis and spectroscopic characterisation of some representative N-alkyl-substituted quaternary ammonium salts derived from benzothiazole, benzoxazole, benzo-selenazole, indole and quinoline are described. These heterocyclic salts, bearing an activated methyl group in the 2-position in relation to the nitrogen atom and N-methyl, -pentyl, -hexyl and -decyl chains, are typical precursors of cyanine dyes.

Full text of DOI:10.3390/70300320

Molecules 2002, 7, 320-330
molecules
ISSN 1420-3049
http://www.mdpi.org
Synthesis and Spectroscopic Characterisation of N-Alkyl
Quaternary Ammonium Salts Typical Precursors of Cyanines
A. C. Pardal1, S. S. Ramos2, P. F. Santos1, L. V. Reis1 and P. Almeida2,*
1 Departamento de Química, Universidade de Trás-os-Montes e Alto Douro, Apartado 202, 5001-911
Vila Real Codex, Portugal. Tel. 351(259)350273, Fax 351(259)350480
2 Departamento de Química e Unidade de Materiais Têxteis e Papeleiros, Universidade da Beira
Interior, Rua Marquês d'Ávila e Bolama, 6200-001 Covilhã, Portugal. Tel. 351(275)319761, Fax
351(275)319730
* Author to whom correspondence should be addressed; e-mail: pjsa@alpha2.ubi.pt
Received: 23 October 2001; in revised form 18February 2002 / Accepted: 26 February 2002 /
Published: 31 March 2002
Abstract: The synthesis and spectroscopic characterisation of some representative N-alkyl-
substituted quaternary ammonium salts derived from benzothiazole, benzoxazole, benzo-
selenazole, indole and quinoline are described. These heterocyclic salts, bearing an activated
methyl group in the 2-position in relation to the nitrogen atom and N-methyl, -pentyl, -hexyl
and -decyl chains, are typical precursors of cyanine dyes.
Keywords: Heterocyclic quaternary ammonium salts, cyanines precursors, spectroscopic
characterisation.
Introduction
Despite the fact that several N-alkyl quaternary ammonium salts bearing a 2-methylbenzothiazole,
-benzoselenazole, -benzoxazole, -indole and -quinoline nuclei are easily found in the literature, mainly
as unisolated precursors of cyanine dyes [1-3], their full physical and spectroscopic characterisation is

Molecules 2002, 7
321
not usually described. To the best of our knowledge, for some of those most commonly used for the
synthesis of cyanines, namely the N-ethyl, -pentyl, -hexyl and -decyl substituted ones, only the
13
1H-NMR spectral data for the N-ethyl quaternary salts [4,5] and the C-NMR spectral data for the N-
ethylquinolinium salts [5] are available.
The 2-methylheterocyclic ammonium salts are generally synthesised by heating the corresponding
heteroaromatic base with a molar equivalent or an excess of an alkylating agent such as an alkyl iodide,
bromide, sulphate or tosylate, among others [1]. Alternatively, the condensation can be carried out in a
polar aprotic solvent as acetonitrile [6] or N,N-dimethylformamide (DMF) [7,8].
Results and Discussion
The N-alkyl-2-methylbenzothiazolium (6a-d), -benzoselenazonium (7a-d), -benzoxazolium (8a-d),
-indolium (9a-d) and -quinolinium (10a-d) quaternary iodides were prepared by heating under reflux a
solution of the corresponding 2-methylheterocyclic base (1-5) with an excess of iodoethane, 1-iodo-
pentane, 1-iodohexane or 1-iododecane in acetonitrile (Scheme 1). The resulting salts were readily
separated from the crude reaction mixtures by precipitation upon addition of diethyl ether. The
alkylating procedure could be repeatedly applied to the mother liquors, each time previously freed of
the precipitation solvent, in order to achieve convenient yields. According to NMR spectroscopy the
products were of satisfactory purity and, therefore, no attempts at further purification by
recrystallization were necessary.
Scheme 1. Synthesis of N-alkyl quaternary ammonium salts 6-10.
X
N
X
RI
CH3CN, reflux
N
R
I
1 X = S
6a-d X = S
2 X = Se
3 X = O
7a-d X = Se
8a-d X = O
4 X = C(CH3)2
9a-d X = C(CH3)2
5 X = CH=CH
10a-d X = CH=CH
a: R = CH2CH3; b: R = (CH2)4CH3; c: R = (CH2)5CH3; d: R = (CH2)9CH3
The quaternary iodides were generally obtained in rather good yields, usually decreasing as the
length of the N-alkyl chain increases (Table 1, see Experimental). The corresponding melting point

Molecules 2002, 7
322
(m.p.), Fourier Transform Infrared Spectra (FTIR) and High Resolution Fast Atom Bombardment Mass
Spectra (HR FAB-MS) data are also collated in Table 1.
The most intense and/or characteristic bands of the FTIR spectra appeared around 3000 cm-1 (C-H
from Ar-H stretch), 2826-2994 cm-1 (C-H from CH2 stretch), 1635-1578 (C=C), 1509-1524 cm-1
(C=N), 1428-1467 cm-1 (CH3 asymmetric deformation and CH2 deformation) and 757-781 cm-1
(skeletal “out of plane” vibration). These last two bands are generally the most intense ones found in
the spectra of the benzoazole and indole salts. For each series of compounds, the intensity of the
aliphatic C-H absorption bands within the 2826-2994 cm-1 region was observed to increase with the
length of the N-alkyl chain.
The 1H- and 13C-NMR spectral data of all the heteroaromatic salts synthesised are collated in Tables
2-5. The NMR spectra were recorded in DMSO-d6 solutions except those of the benzoxazolium salts
8a-d, which were recorded in CDCl3 solution, since in the latter solvent an unexpected transformation
was observed. This result is currently the subject of a separate study, the results of which shall be
published elsewhere.
1
13
The assignment of the aromatic H- and C-NMR signals was based on their chemical shifts and
1
multiplicity (for the H signals) and was unambiguously established with the aid of HMQC
(Heteronuclear Multiple Quantum Coherence), HMBQ (Heteronuclear Multiple Bond Correlation) and
1
COSY (Correlated Spectroscopy) experiments. The attributions of the aromatic H-NMR chemical
shifts are in full agreement with those previously reported for the N-ethyl quaternary salts derived from
the same heteroaromatic bases employed herein [4,5]. The assignments of the aromatic 13C- signals are
also consistent with the spectral data of salts similar to 6-9 [9-12] and with that described for N-ethyl-
1
2-methylquinolinium iodide (10a) [5]. The assignment of the aliphatic H- and 13C-NMR chemical
shifts was accomplished based on the deshielding effect displayed by the neighbouring electronegative
nitrogen atoms [13].
1
The H-NMR absorptions of the 2-CH3 groups typically range from 2.84 to 3.36 ppm. The salts
derived from 2,3,3-trimethylindole (4) invariably display the lowest chemical shift, coincidentally the
same for compounds 9a-d, once the deshielding effect of the heteroatoms of benzoazoles 6-8 and that
of the sp2 carbon in the quinolinium salt 10 are absent.
The 13C-NMR chemical shifts of 2-C fall within the 13.7-19.9 ppm region. Accordingly to the
reasons afore mentioned, the lower field absorptions are ascribed to the substituted indolium salts 9a-d.
The order of the aromatic 13C chemical shifts show a clear dependence on the nature of the
heterocyclic moiety of the salt, being in almost every cases different from one salt to another. Only the
2-C absorption is, for all compounds, the one at lower field as a consequence of being, simultaneously,
sp2 hybridised and adjacent to a positively charged nitrogen (Table 5). On the contrary, the order of the
chemical shifts of the aromatic protons is the same for compounds 6-9, when their relative position
with respect to the nitrogen atom of the heterocyclic moiety is considered. An exception to this trend is
observed for the quinolinium salts 10a-d where the absorption of the 5-H appears at higher field than
that of 8-H.

Molecules 2002, 7
323
Conclusions
The synthesis and spectroscopic characterisation of some representative ammonium quaternary
salts, bearing benzothiazole, benzoxazole, benzoselenazole, indole and quinoline nuclei, possessing a
methyl group in the 2-position in relation to the ammonium group and methyl, pentyl, hexyl and decyl
N-alkyl chains was described.
Acknowledgements
Thanks are due to FCT, Lisbon, POCTI and FEDER for their financial support for this work
(Project POCTI/32915/QUI/00).
Experimental
General
All reagents and chemicals were obtained from Sigma-Aldrich. Solvents were of analytical grade.
Reactions were monitored by thin-layer chromatography using 0.20 mm aluminium-backed silica-gel
plates (Merck GF254). The plates were eluted with dichloromethane/methanol (5-10%) and the spots
examined under 254, 312 and 365 nm UV light. Melting points were measured in open capillary tubes
in a Büchi 530 apparatus and are uncorrected. FTIR spectra were recorded on a Mattson 5000
spectrophotometer. All samples were prepared by mixing FTIR-grade KBr (Sigma-Aldrich) with 1%
(w/w) salt, and grinding to a fine powder. Spectra were recorded over the 400-4000 cm-1 range without
1
baseline corrections. Characteristic absorptions are given in cm-1. H- and 13C-NMR spectra were
recorded in DMSO-d6 or CDCl3 solutions on a Brüker ACP 250 (250.13 and 62.90 MHz), a Brüker
ARX 400 (400.13 and 100.62 MHz) or a Brüker ARX 500 Avance spectrometer (500.13 and 125.76
MHz). Chemical shifts are reported as δ values in ppm using TMS as an internal standard. Coupling
constants (J) are given in Hz. HMQC, HMBC and COSY experiments were performed on the Brüker
ARX 400 spectrometer. High Resolution Fast Atom Bombardment Mass Spectra (HR FAB-MS) were
recorded in a Micromass AutoSpec M, operating at 70 eV, using a matrix of 3-nitrobenzyl alcohol.
Synthesis of quaternary ammonium salts 6-10
A solution of the heteroaromatic compound [2-methylbenzothiazole (1), 2-methylbenzoselenazole
(2), 2-methylbenzoxazole (3), 2,3,3-trimethylindole (4) or 2-methylquinoline (5)] (1.0 mmol) and the
appropriate alkylating agent (iodoethane, 1-iodopentane, 1-iodohexane or 1-iododecane) (3.0-5.0
mmol) in acetonitrile (25 mL) was heated under reflux for 24 h. After cooling, diethyl ether was added,
the desired quaternary salts 6-10 collected by filtration under reduced pressure and washed several

Molecules 2002, 7
324
times with diethyl ether. Drying under vacuum furnished spectroscopically pure compounds 6-10. The
ether from the combined filtrates was removed by evaporation at reduced pressure and the remaining
residue, consisting mainly of the unreacted starting materials, was heated under reflux for another 24 h
and worked-up as described above. The process was repeated 1-3 times to achieve a suitable yield.
Yields, m.p. and spectroscopic data of the compounds thus prepared is collated in Tables 1-5.
Table 1. Yields, m.p., FTIR and HR FAB-MS spectral data of salts 6-10.
Salt Yield m.p. (ºC)
FTIR
HR FAB-MS m/z found
(M. formula: calcd.)
λmax (cm-1)
(%)
(Lit.)
198-199
178.068281
78
59
44
39
2970, 2915, 1578, 1513, 1445, 1330, 779
6a
6b
6c
6d
(219)[14]
(C10H12NS: 178.069046)
220.115129
2957, 2908, 2861, 1578, 1521, 1461, 1442,
1333, 768
152-153
(C13H18NS: 220.115997)
234.130630
2956, 2925, 2871, 2853, 1579, 1520, 1459,
1440, 1338, 763
125-126
111-112
(C14H20NS: 234.131647)
290.194478
2921, 2859, 1581, 1517, 1464, 1441, 1336, 770
(C18H28NS: 290.194247)
224.015196/226.014502
(C10H12N78Se: 224.014278;
C10H12N80Se: 226.013495)
266.060980/268.060429
(C13H18N78Se: 266.061229;
C13H18N80Se: 268.060445)
280.077788/282.076779
(C14H20N78Se: 280.076879;
C14H20N80Se: 282.076095)
336.139687/338.139261
(C18H28N78Se: 336.139479;
C18H28N80Se: 338.138696)
162.091907
212-213
69
47
40
25
2971, 2920, 1579, 1509, 1445, 1320, 1191, 777
7a
7b
7c
(212)[15]
2952, 2920, 2864, 1576, 1515, 1441, 1369,
1326, 1188, 770
163-164
132-133
140-141
2953, 2932, 2858, 1578, 1516, 1457, 1440,
1325, 1185, 757
2921, 2852, 1579, 1514, 1457, 1442, 1324,
1189, 757
7d
195-197
58
41
35
28
2979, 1599, 1461, 1389, 766
2953, 2933, 2867, 1588, 1461, 1392, 765
2954, 2921, 2852, 1590, 1462, 1390, 766
2921, 2852, 1589, 1461, 1391, 765
8a
8b
8c
8d
(195-197)[16]
(C10H12NO: 162.091889)
204.139504
103-105
90-91
(C13H18NO: 204.138839)
218.154355
(C14H20NO: 218.154489)
274.217316
83-85
(C18H28NO: 274.217090)

Molecules 2002, 7
325
188.144234
59
50
46
46b)
73
65
46
37
226-228
138-139
2972, 1635, 1459, 1437, 773
2953, 2935, 2867, 1626, 1463, 769
2967, 2933, 2856, 1623, 1467, 1455, 769
2925, 2856, 1625, 1607, 1461, 765
9a
9b
(C13H18N: 188.143925)
230.191539
(C16H14N: 230.190875)
224.207536
146-147
9c
(C17H26N: 224.206525)
300.268937
9da)
10a
10b
10c
10d
viscous oil
(C21H34N: 300.269125)
172.113046
238-239
2994, 2925, 1603, 1521, 1436, 1363, 1344, 1150,
828, 786
(237-39)[17]
(C12H14N: 172.112625)
214.160311
2947, 2931, 2869, 1603, 1523, 1428, 1367, 1347,
1172, 781
156-157
129-130
118-120
(C15H20N: 214.159575)
228.175540
2948, 2913, 2868, 2826, 1604, 1524, 1428,
1373,1359, 825, 779
(C16H22N: 228.175225)
284.238820
2917, 2853, 1609, 1522, 1472, 1424, 1365,
816, 778
(C20H30N: 284.237825)
a) FTIR spectrum: film in NaCl; b) Isolated by column chromatography (silica; 0 to 5% - CH2Cl2/MeOH)
Table 2. Aliphatic 1H-NMR spectral data of quaternary ammonium salts 6-10 (DMSO-d6).
δ (ppm), multiplicity, J (Hz)
Salt
(Lit. value)[reference]
a
b
N-ethyl (N-CH2 CH3 )
a
b
CH2
CH3
2-CH3
3.23, s
C(CH3)2
4.78, q, 7.0 1.46, t, 7.0
(4.74)[4] (1.49)[4]
4.74, q, 7.0 1.44, t, 7.0
(4.63)[4] (1.40)[4]
4.73, q, 7.5 1.63, t, 7.5
(4.60)[4] (1.51)[4]
4.50, q, 7.0 1.44, t, 7.0
(4.63)[4]c) (1.66)[4]c)
5.01, q, 7.0 1.54, t, 7.0
6aa)
7aa)
-
(3.22)[4]
3.24, s
-
-
(3.15)[4]
3.36, s
8aa),b)
9aa)
(3.12)[4]
2.84, s
(3.10)[4]c)
1.53, s
3.13, s
10d)
-
(4.95)[4]
(5.03)[5]
(1.52)[4]
(1.54)[5]
(3.10)[4]
(3.15)[5]

Molecules 2002, 7
326
a
b
c
d
e
N-pentyl (N-CH2 H2 CH2 CH2 CH3 )
a
b
c
d
e
CH2
CH2
CH2
CH2
CH3
2-CH3
3.23, s
3.25, s
3.38, s
2.84, s
3.12, s
C(CH3)2
6bd)
7be)
8ba),b)
9ba)
4.72, t, 7.5 1.86, qt, 8.0 1.40-1.46, m 1.35, sext, 7.5 0.89, t, 7.0
-
4.68, t, 8.0 1.82, qt, 8.0
4.69, t, 8.0 2.00, qt, 7.5
4.45, t, 7.5 1.84, qt, 7.5
4.92, t, 8.0 1.90, qt, 8.0
1.25-1.47, m
1.34-1.44, m
1.30-1.44, m
0.86, t, 7.0
0.87, t, 7.0
0.88, t, 7.0
-
-
1.55, s
-
10bd)
1.55, qt, 7.5
1.40, sext, 7.5 0.92, t, 7.0
a
b
c
d
e
f
N-hexyl (N-CH2 CH3 CH2 CH2 CH2 CH3 )
a
b
c
d
e
f
CH2
CH2
CH2
CH2
CH2
CH3
2-CH3
C(CH3) 2
6ca)
7ca)
8ca),b)
9ca)
4.71, t, 8.0 1.84, qt, 8.0 1.44, qt, 7.5
4.67, t, 8.0 1.83, qt, 8.0 1.44, qt, 7.5
4.66, t, 7.5 1.99, qt, 7.5 1.43, qt, 7.5
4.46, t, 8.0 1.83, qt, 8.0 1.42, qt, 7.5
4.91, t, 8.0 1.88, qt, 8.0 1.56, qt, 7.5
1.26-1.34, m
1.25-1.35, m
1.24-1.33, m
1.24-1.34, m
1.29-1.37, m
0.87, t, 7.0
0.87, t, 7.0
0.83, t, 7.0
0.86, t, 7.0
0.89, t, 7.0
3.22, s
3.22, s
3.36, s
2.86, s
3.12, s
-
-
-
1.54, s
-
10ca)
a
b
c
d
e
f
g
h
i
j
N-decyl (N-CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH3 )
a
b
c
d
e-i
j
CH2
4.72, t, 8.0 1.84, qt, 8.0 1.44, qt, 7.5 1.32, qt, 7.0
4.67, t, 8.0 1.81, qt, 8.0 1.43, qt, 7.5 1.20-1.32, m
CH2
CH2
CH2
CH2
CH3
2-CH3 C(CH3)2
6dd)
7da)
0.85, t, 7.0 3.24, s
0.84, t, 7.0 3.22, s
-
1.25-1.28, m
-
8da),b)
9da)
10dd)
4.70, t, 7.5 2.00, qt, 7.5 1.44, qt, 7.5 1.33, qt, 7.0 1.22-1.28, m 0.85, t, 7.0 3.39, s
4.46, t, 7.5 1.83, qt, 7.5 1.41, qt, 7.0 1.22-1.32, m 0.83, t, 6.5 2.86, s
-
1.54, s
-
4.91, t, 8.0 1.88, qt, 8.0 1.56, qt, 7.5 1.36, qt, 7.0 1.26-1.28, m 0.86, t, 7.0 3.11, s
a) At 400.13 MHz; b) in CDCl3; c) in DMSO-d6/D2O (3/5); d) at 500.13 MHz; e) at 250.13 MHz.
Table 3. Aromatic 1H-NMR spectral data of quaternary ammonium salts 6-10 (DMSO-d6).
1
4
4
7
3
5
3a
7a
3a
4a
8a
6
5
X
5
6
6
7
3
2
2
7a N 1
R
N 3
R
2
N1
R
4
7
8
I
I
I
6-8
9
10

Molecules 2002, 7
327
δ (ppm), multiplicity, J (Hz)
Salt
(Lit. value)[reference]
benzothiazolium
4-H
5-H
6-H
7-H
6aa)
8.35, d, 8.0
(8.28)[4]
7.89, dt, 7.5; 1.0
(7.86)[4]
7.80, dt, 7.5; 1.0
(7.77)[4]
8.42, d, 8.0
(8.39)[4]
6bb)
6ca)
6db)
8.36, d, 8.5
8.34, d, 8.5
8.36, d, 8.5
7.90, dt, 7.5; 1.0
7.89, dt, 8.0; 1.0
7.81, dt, 7.5; 1.0
7.81, dt, 7.5; 1.0
7.80, t, 7.5
8.47, d, 8.0
8.46, d, 8.0
7.90, dt, 8.0; 1.0
8.48, dd, 8.0; 1.0
benzoselenazolium
7aa)
4-H
5-H
6-H
7-H
8.31, d, 8.0
(8.18)[4]
7.82, dt, 7.5; 1.0
(7.71)[4]
7.72, dt, 7.5; 1.0
(7,61)[4]
8.51, dd, 8.0; 1.0
(8.36)[4]
7bc)
7ca)
7da)
8.31, d, 8.0
8.30, d, 8.0
8.30, d, 8.0
7.81, t, 7.5
7.70, t, 7.5
8.54, d, 8.0
7.83, dt, 7.5; 1.0
7.82, dt, 7.5; 1.0
7.72, dt, 7.5; 1.0
7.72, dt, 7.5; 1.0
8.45, dd, 8.0; 1.0
8.48, dd, 8.0; 1.0
benzoxazolium
8aa),d)
4-H
5-H
5-H
6-H
7-H
7.80-7.78, m
7.68-7.65, m
7.98-7.96, m
(8.09)[4]
7.83-7.81, m
7.90-7.88, m
7.91-7.89, m
(7.74)[4]
(7.75)[4]
(8.16)[4]
7.92-7.90, m
7.82-7.80, m
7.84-7.81, m
8ba),d)
8ca),d)
8da),d)
7.71-7.68, m
7.69-7.67, m
7.72-7.67, m
4-H
6-H
7-H
indolium
9aa)
7.96-7.99, m
(8.00)[4]e)
7.62-7.64, m
(7.79)[4]e)
7.84-7.86, m
(7.93)[4]e)
9ba)
9ca)
9da)
7.96-7.98, m
7.97-8.00, m
7.98-8.00, m
7.60-7.65, m
7.60-7.65, m
7.60-7.64, m
7.82-7.86, m
7.83-7.86, m
7.84-7.87, m
3-H
4-H
5-H
6-H
7-H
8-H
quinolinium
10ab)
8.14, d, 8.5
(8.14)[5]
9.12, d, 8.5
(9.13)[5]
8.43, dd, 8.0; 1.0
(8.27)[5]
8.00, t, 7.5
(8.03)[5]
8.25, dt, 8.0; 1.0
(8.10)[5]
8.63, d, 9.0
(8.64)[5]
10bb)
10ca)
10db)
8.14, d, 8.5
8.13, d, 8.5
8.12, d, 8.5
9.11, d, 8.5
9.11, d, 8.5
9.10, d, 8.5
8.42, dd, 8.0; 1.0
8.41, dd, 8.0; 1.0
8.41, dd, 8.0; 1.0
8.00, t, 7.5
7.99, t, 7.5
8.00, t, 7.5
8.24, dt, 8.0; 1.0
8.23, dt, 8.0; 1.0
8.23, dt, 8.0; 1.0
8.59, d, 9.0
8.59, d, 9.0
8.59, d, 9.0
a) At 400.13 MHz; b) at 500.13 MHz; c) at 250.13 MHz; d) in CDCl3; e) in DMSO-d6/D2O (3/5).

Molecules 2002, 7
Table 4. Aliphatic 13C-NMR spectral data of quaternary ammonium salts 6-10 (DMSO-d6).
328
δ (ppm)
Salt
(Lit. value)[reference]
N-ethyl (N-CaH2CbH3)
CaH2
CbH3
2-CH3
C(CH3)2
6aa)
7aa)
8aa),b)
44.7
45.6
13.2
13.0
14.0
12.6
13.3
16.8
19.5
16.7
13.7
22.3
-
-
-
44.4
9aa)
43.0
21.8
47.1
10a)
-
(47.26)[5]
(13.43)[5] (22.44)[5]
N-pentyl (N-CaH2CbH2CcH2CdH2CeH3)
CaH2
CbH2
CcH2
CdH2
CeH3
2-CH3
C(CH3)2
6bc)
7bc)
8ba),b)
9ba)
49.2
50.1
49.1
47.3
51.5
28.1
28.0
28.6
27.8
28.0
27.6
27.4
27.9
26.7
27.8
21.8
21.8
22.0
21.5
21.8
13.8
13.8
13.7
13.5
13.9
17.1
19.9
16.7
13.8
22.7
-
-
-
21.8
-
10bc)
N-hexyl (N-CaH2CbH2CcH2CdH2CeH2CfH3)
CaH2
CbH2
CcH2
CdH2
CeH2
CfH3
2-CH3
C(CH3)2
6ca)
7ca)
8ca),b)
9ca)
49.1
50.0
49.0
47.5
51.3
30.6
30.6
31.0
30.6
30.6
27.7
27.6
28.1
27.1
27.9
25.4
25.4
26.3
25.4
25.4
21.8
21.9
22.2
21.9
21.9
13.8
13.8
13.8
13.7
13.7
16.8
19.5
16.7
14.0
22.4
-
-
-
21.7
-
10ca)
N-decyl (N-CaH2CbH2CcH2CdH2CeH2CfH2CgH2ChH2CiH2CjH3)
CaH2
CbH2
CcH2
Cd-iH2
CjH3
2-CH3
C(CH3)2
6dc)
7da)
8da),b)
9da)
49.3
50.0
49.2
47.6
51.5
31.2
31.1
31.7
31.1
31.3
28.9
28.7
29.3
28.7
28.9
28.7, 28.6, 27.8, 25.9, 22.1
28.5, 28.4, 27.5, 25.7, 21.9
13.9
13.8
14.0
17.3
19.6
16.7
-
-
29.2, 29.1, 28.9, 28.2, 26.7, 22.5
-
21.9
-
28.5, 28.4, 27.1, 25.7
13.8, 14.1
10dc)
28.7, 28.6, 28.1, 25.9, 22.1
14.0
22.6
a) At 100.6 MHz; b) in CDCl3; c) at 62.9 MHz.

Molecules 2002, 7
Table 5. Aromatic 13C NMR spectral data of quaternary ammonium salts 6-10 (DMSO-d6).
329
δ (ppm)
Salt
(Lit. value)[reference]
benzothiazolium
2-C
3a-C
4-C
5-C
6-C
7-C
7a-C
6aa)
6bb)
6ca)
6db)
176.7
177.0
176.9
176.8
140.4
140.8
140.7
140.7
116.6
116.9
116.8
116.9
129.3
129.4
129.3
129.3
127.9
128.1
128.0
128.0
124.6
124.7
124.6
124.7
129.9
129.1
129.0
129.0
benzoselenazolium
7aa)
2-C
3a-C
4-C
5-C
6-C
7-C
7a-C
187.9
141.4
118.1
128.6
127.5
127.6
131.8
7bb)
7ca)
7da)
188.0
188.1
188.0
141.8
141.8
141.7
118.4
118.4
118.3
128.7
128.7
128.6
127.6
127.3
127.3
127.7
127.7
127.6
131.8
131.8
131.8
benzoxazolium
8aa),c)
2-C
3a-C
4-C
5-C
6-C
7-C
7a-C
167.0
147.8
113.2
129.1
128.3
114.5
129.2
8ba),c)
8ca),c)
8da),c)
167.3
167.2
167.3
147.9
147.8
147.9
113.3
113.3
113.3
129.3
129.3
129.3
128.4
128.4
128.4
114.5
114.4
114.5
129.6
129.6
129.7
indolium
2-C
3-C
3a-C
4-C
5-C, 6-C
7-C
7a-C
9aa)
9ba)
9ca)
9da)
196.0
196.3
196.3
196.2
54.0
54.1
54.0
54.0
141.8
141.8
141.7
141.7
115.2
115.2
115.4
115.4
128.8, 129.3
128.7, 129.2
128.8, 129.3
128.8, 129.3
123.4
123.3
123.4
123.4
140.6
141.0
141.0
140.9
quinolinium
10aa)
2-C
3-C
4-C
4a-C
5-C
6-C
7-C
8-C
8a-C
160.4
125.4
145.5
128.1
130.5
128.9
135.2
118.7
137.9
(160.40)[5] (125.49)[5] (145.51)[5] (128.25)[5] (118.75)[5] (128.98)[5] (135.26)[5] (130.57)[5] (138.07)[5]
10bd)
10ca)
10dd)
160.5
160.4
160.6
125.6
125.4
125.6
145.6
145.5
145.6
128.2
128.1
128.2
130.6
130.4
130.6
129.0
128.9
129.0
135.3
135.2
135.3
119.0
118.8
119.0
138.2
138.1
138.2
a) At 100.6 MHz; b) at 62.9 MHz; c) in CDCl3; d) at 125.76 MHz.

Molecules 2002, 7
330
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2.
3.
4.
5.
6.
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8.
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Sample Availability: Available from the authors.
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