Combination of pyridinium and isoquinolinium ylides with phenylisocyanate and isothiocyanates: Synthesis, characterisation, and X-ray crystal structures of mesoionic monosubstituted 3-oxo-propanamides or thioamides

Article abstract of DOI:10.1071/CH15113

Pyridinium ylides derived from 2-bromoacetophenone or methyl bromoacetate have been reacted with phenylisocyanate, phenyl- or methylisothiocyanate to afford mesoionic monosubstituted 3-oxo-propanamides or thioamides, via self-protonation of the intermedia

Full text of DOI:10.1071/CH15113

CSIRO PUBLISHING
Aust. J. Chem.
Full Paper
http://dx.doi.org/10.1071/CH15113
Combination of Pyridinium and Isoquinolinium Ylides
with Phenylisocyanate and Isothiocyanates: Synthesis,
Characterisation, and X-Ray Crystal Structures
of Mesoionic Monosubstituted 3-Oxo-Propanamides
or Thioamides
A
B
C
Mohammad Seifi, S. Yousef Ebrahimipour, Jim Simpson,
D
D
,
B E
Michal Dusek, Vaclav Eigner, and Hassan Sheibani
A
Department of Chemistry, Faculty of Science Najafabad Branch,
Islamic Azad University, Najafabad, Esfahan, Iran.
B
Department of Chemistry, Shahid Bahonar University of Kerman, Kerman 76169, Iran.
C
Department of Chemistry, University of Otago, PO Box 56, Dunedin 9054,
New Zealand.
D
Institute of Physics of the ASCR, v.v.i., Na Slovance 2, 182 21 Prague 8,
Czech Republic.
E
Corresponding author. Email: hsheibani@mail.uk.ac.ir
Pyridinium ylides derived from 2-bromoacetophenone or methyl bromoacetate have been reacted with phenylisocyanate,
phenyl- or methylisothiocyanate to afford mesoionic monosubstituted 3-oxo-propanamides or thioamides, via self-
protonation of the intermediate N-anion. A similar reaction under the same conditions of isoquinolinium ylides with
phenylisocyanate or phenyisothiocyante also produced the corresponding mesoionic compounds. In order to establish the
exact structure of the mesoionic compounds, single crystal X-ray structures were obtained for three of the pyridinium
ylides.
Manuscript received: 7 March 2015.
Manuscript accepted: 24 April 2015.
Published online: 3 June 2015.
Introduction
[12–15]
heterocyclic derivatives. Combination of these ylides with
Michael acceptors as electron-deficient reagents along with ring
Conjugated heterocyclic N-ylides are used as building blocks for
a wide range of fused heterocyclic compounds due to their 1,3-
dipolar character.
reactions such as cycloaddition reactions of (chlorocarbonyl)
closure strategies (cyclisation) is the most useful methodology
[16]
[
1–3]
This character has been observed in many
for preparing three- or five-membered rings.
Pyridinium
ylides are a special variety of ammonium ylides, which can react
with alkenes substituted with electron-withdrawing groups to
[
4–6]
ketenes with 1,2- and 1,3-dinucleophiles.
In the preparation
[
17,18]
of heterocyclic compounds, cycloimmonium ylides such
as pyridinium and isoquinolinium ylides have been used
extensively. The positively charged nitrogen atom of an aza-
heterocyclic compound can be covalently bonded to such
zwitterionic ylides. These ylides are zwitterions in which a
carbanion is covalently bonded to a positively charged nitrogen
give the corresponding cyclopropanes.
Also the pyridine
group has been utilized as a leaving group in intermolecular
reactions. However the 1,3-dipolar cycloaddition of heteroaro-
matic N-ylides, such as isoquinolinium ylides with electron-
deficient alkynes and alkenes resulted in the formation of
[
7]
[
19–21]
pyrrolo isoquinoline derivatives.
have great potential for use as analytical reagents and as
In addition these ylides
[3]
[1]
atom from the azaheterocycle. Generally, cycloimmonium
ylides are unstable except when two electron-withdrawing
groups are introduced on the carbanion. The negative charge at
the ylidic carbanion centre is known to be the source of nucle-
ophile behaviour by these ylides. This is also responsible for
their ability to behave as mono- or bidentate ligands towards
[
16]
semiconducting materials, and some of them have also shown
[
17]
biological activity. Cycloimmonium ylides are also used in
the synthesis of ylidic polymers by interphase-transfer poly-
condensation reactions. As a continuation of our interest in
the synthesis of mesoionic compounds by the reactions of
[
18]
[8–11]
[4–6]
metal ions.
Pyridinium and isoquinolinium salts derived
(chlorocarbonyl)ketenes with 1,3-dinucleophiles,
we wish
from a-halogenocarbonyl compounds are easily deprotonated to
give the corresponding ylides, which find wide applications in
the formation of three- and five-membered ring heterocycles
such as cyclopropane and isoxazole, and 6-membered ring
to report the reactions of pyridinium and isoquinolinium ylides
with phenylisocyanate and isothiocyanates leading to the
synthesis of a variety of mesoionic compounds. These reactions
produced the pyridinium or isoquinolinium methylides 3a–f and
Journal compilation Ó CSIRO 2015
www.publish.csiro.au/journals/ajc

B
M. Seifi et al.
O
R
ꢃ
ꢃ
N
ꢀ
..
O
N
H
CH CN
Route A
O
ꢃ
ꢀ
3
R
..
N
ꢃ
Rꢂ-NꢁCꢁX
2a–c
R
Et
N
3
B
N
H
Br
X
X
A
ꢀ
Rꢂ
:
N
Rꢂ
1
a–b
3a–f
I
3
3
3
3
a: R ꢁ Ph, Rꢂ ꢁ Ph, X ꢁ O, (95 %)
Route B
ꢀ
b
: R ꢁ OCH , Rꢂ ꢁ Ph, X ꢁ O, (93 %)
N
3
c: R ꢁ Ph, Rꢂ ꢁ Ph, X ꢁ S, (90 %)
: R ꢁ OCH , R ꢁ Ph, X ꢁ S, (93 %)
d
3
O
R
X
3e: R ꢁ Ph, Rꢂ ꢁ CH , X ꢁ S, (90 %)
3
H
3f: R ꢁ OCH , Rꢂ ꢁ CH , X ꢁ S, (90 %)
3
3
N
Rꢂ
II
Not formed
Scheme 1.
O
ꢃ
O
N
H
R
CH CN
Route A
ꢃ
N
ꢃ
3
ꢀ
..
R
N
ꢃ
Ph
N
C
X
ꢀ
R
Et N
3
O
..
Br
A
X
B
ꢀ
N
H
X
:
N
Ph
Ph
4
a–b
2a–b
5a–c
II
Route B
5
5
5
a: R ꢁ Ph, Rꢂ ꢁ Ph, X ꢁ O, (96 %)
: R ꢁ Ph, Rꢂ ꢁ Ph, X ꢁ S, (95 %)
c: R ꢁ OCH , Rꢂ ꢁ Ph, X ꢁ O, (93 %)
b
3
O
N
R
N
Ph
X
Not formed
Scheme 2.
5
a–c (Schemes 1 and 2) with two electron-withdrawing groups
on the carbanion in excellent yields (90–96 %). Structures of
a–f and 5a–c were confirmed by elemental analysis and
Table 1. Solvent and base effects on the reaction of pyridinium or
isoquinolinium bromides with phenylisocyanate
3
spectroscopic data; structures of ylides 3b–d were also estab-
lished by X-ray crystallography.
Comp. no.
Solvent
Base
Et
Time [min]
Yield [%]
3a
3a
3a
3a
3a
3a
5a
5a
5a
5a
5a
Acetonitrile
Acetonitrile
Toluene
3
N
15
18
30
25
20
25
12
15
25
22
18
22
95
92
90
92
90
88
96
90
88
90
87
85
K
2
CO
3
3
3
3
3
3
Results and Discussion
Et
3
N
Toluene
K
2
CO
We began our study by examining the reactivity of N-ylides
derived from pyridinium and isoquinolinium bromides with
activated double bonds. First we investigated the reaction of the
pyridinium salts 1a, b with phenylisocyanate 2a and phenyl or
methylisothiocyanates 2b and 2c in the presence of triethyl-
amine, which yielded the 1,3-dioxo-2-(pyridin-1-ium-1-yl)
propan-2-ide and 1-oxo-2-(pyridin-1-ium-1-yl)-3-thioxopropan-
CH
CH
2
Cl
Cl
2
Et
3
N
2
2
K
2
CO
Acetonitrile
Acetonitrile
Toluene
Et
3
N
K
2
CO
Et
3
N
Toluene
K
2
CO
CH
2
Cl
2
3
Et N
2
-ide derivatives 3a–f, respectively.
The mechanism of the reaction involves the base induced
5a
CH Cl
2
2
K CO
2
formation of an intermediate N-anion I (Scheme 1). This under-
goes facile self-deprotonation (Route A) to yield the mesoionic
products 3a–f in excellent yields (Table 1). Interestingly, the
alternative cyclisation reaction (Route B) resulting from loss of
pyridine from the N-anion is not observed in this case.
The corresponding reactions of isoquinolinium ylides (4a,
b), prepared in situ from the reaction of isoquinolinium bro-
mides, with phenylisocyanate or phenylisothiocyanate 2a, b
gave the analogous 2-(1,3-dioxo or 1-oxo-3-thiopropan-2-yl)

Pyridinium and Isoquinolinium Ylides
C
O1w
isoquinolin-2-ium derivatives 5a–c again as mesoionic com-
pounds and in high yields. A similar mechanism (Scheme 2)
involving an intermediate isoquinolinium-N-anion is believed to
be involved in the reaction with cyclisation to a dihydroimidazo
C12
C11
C15
C10
O3
[2,1-a]isoquinolin-2(3H)-one or thione disfavoured. Gololobov
et al.
C13
[22]
have reported that the reaction of pyridinium ylides
C14
C3
N2
derived from the reaction of a malonic ester with isocyanates
leads to reversible C # N migration of the ethoxycarbonyl
group with the formation of the corresponding carbamates in an
unexpected way. In conjunction with our observations, it is
interesting to note that reversible C # N migration of the
benzoyl or methoxycarbonyl groups has not occurred in the
reactions reported here. In order to optimise the reaction condi-
tions, we used both polar and non-polar solvents in the reaction
of pyridinium or isoquinolinium bromides with phenylisocya-
nate in the presence of either triethylamine or potassium
carbonate as the base. The results are shown in Table 1. It is
noteworthy that polar solvents such as acetonitrile and dichlor-
omethane afford better yields with shorter reaction times than
the less polar toluene. Acetonitrile and triethylamine are the
most effective solvent and base, respectively.
C2
C1
O2
O1
N1
C4
C5
C9
C6
C8
C7
3
b
C18
C19
C17
C16
C11
C12
C13
1
According to the infra-red (IR) and H NMR spectroscopic
C20
C10
N2
C15
C3
data, compounds 3a–f and 5a–c show an intramolecular hydro-
gen bond between the NH group of the amide acting as a donor
and the oxygen atom of the ketone or ester acting as an acceptor.
The IR spectra of compounds 3a–f and 5a–c showed the broad
stretching bands of the NH groups in the range of 3450–
C14
C2
C1
O1
S1
ꢀ1
N1
C4
3
and amide groups are found in the region of 1690–1630 cm
300 cm . The carbonyl stretching bands of the ester, ketone,
.
ꢀ1
1
C9
C5
The H NMR spectra of these compounds indicated the proton of
the amide or thioamide groups (NH) appeared as a singlet and
was well downfield (d 14.61–10.62), which is consistent with
H
C6
C8
literature precedents for closely related products.
C7
3
c
X-Ray Crystal Structure
The molecular structures of the three compounds (Fig. 1) have
similar features and they can be sufficiently discussed together.
Each zwitterionic molecule comprises a central amide unit, 3b
C11
C14
C12
C15
C10
O2
(or thioamides 3c or 3d), that forms pyridinium ylides via the
C3
C2–N2 bonds to the pyridinium rings. The amide or thioamide
N1 atoms carry phenyl substituents, while the C2 atoms that
have a formal negative charge have pyridinium and either
C13
N2
O1
C2
C1
1
-oxo-1-methoxy, 3b and 3d or 1-oxo-1-phenyl, 3c, substituents
S1
N1
C4
that combine with the C1 atoms of the amide or thioamide units
to generate propan-2-ide functional groups. Compound 3b
crystallizes with a solvent water molecule in the asymmetric
unit. The O atom of the solvent lies on a 2-fold axis and is linked
to the main molecule by a very weak C15–H1c15ꢁꢁꢁO1w
hydrogen bond. The N1, C1, O1, C2, C3, O2, O3, C15 segment
of 3b is reasonably planar with a root-mean-square (rms)
C5
C9
C6
C7
C8
˚
deviation of 0.0742 A from the best fit plane through all eight
3
d
atoms. The phenyl and pyridinium ring planes subtend dihedral
angles of 24.08(4) and 79.07(4) 8, respectively, to that plane.
Similarly the C4, N1, C1, S1, C2, C3, O1, C15 segments of 3c
and 3d are also almost planar with rms deviations for the eight
Fig. 1. The molecular structures of 3b, 3c, and 3d with ellipsoids drawn at
the 50 % probability level. Intramolecular hydrogen bonds and a C–HꢁꢁꢁO
contact in the asymmetric unit of 3b are drawn as dashed lines.
˚
atoms in the plane of 0.0573 and 0.0772 A respectively. The
corresponding dihedral angles between these planes and the
phenyl and pyrimidine rings of the two molecules are 52.28(5)
and 31.54(4)8 for 3c and 65.57(5) and 73.05(4)8 for 3d. A feature
of all three compounds is the ready formation of strong intra-
molecular N1–H1nꢁꢁꢁO1 hydrogen bonds, that contribute to the
planarity of the central portions of these molecules and form
with no directly comparable compounds of their structures
reported in the Cambridge Structural Database Version 5.35
(November 2013 plus three updates). The database contains
structures both of purely organic pyridinium ylides (ten exam-
[
24]
ples) and of their transition metal complexes (four exam-
[12]
[23]
S(6) rings.
The pyridinium ylides reported here are unique,
ples).
Of these, only the structure of 1-((4-bromophenyl)

D
M. Seifi et al.
1
3
Table 2. Crystallographic data for 3b–d
Bruker spectrometer. C NMR spectra were recorded on the
same instruments at 100 or 75 MHz using TMS as an internal
standard. Mass spectra were measured on a GCMS-QP1000 EX
spectrometer at 70 eV. Elemental analyses were performed
using a Heracus CHN-O-Rapid analyser. Pyridinium and iso-
quinolinium salts were prepared according to a literature
Compound
3b
3c
3d
Empirical formula
MW
2 (C15
H
14
N
2
O
3
)ꢁH
2
O C20
H
16
N
2
14 2 2
OS C15H N O S
558.6
332.4
Monoclinic Monoclinic
C2/c P2 /c
17.6133 (14) 8.9233 (7)
8.8929 (6) 9.3219 (7)
286.3
Crystal system
Space group
˚
a [A]
˚
b [A]
˚
c [A]
Monoclinic
[
28]
procedure.
C2/c
1
11.7956 (11)
14.3714 (12)
16.0591 (15)
100.089 (8)
4
Typical Procedure for the Preparation of Compounds 3a–f
and 5a–c in Acetonitrile
21.5344 (15) 17.0065 (13)
101.973 (6) 93.618 (6)
b [8]
Z
A solution of the pyridinium salts (1a, b) or the isoquinolinium
salts (4a, b) (2 mmol), phenylisocyanate or isothiocyanates
8
4
˚
3
V [A ]
2680.2 (4)
1.384
3299.6 (4)
1.338
0.21
1411.82
1.347
0.23
(2 mmol) and triethylamine (0.2 mL) in acetonitrile (20 mL) was
ꢀ
3
D
calc [g cm
]
stirred at room temperature for ,15 min (the progress of the
reaction was monitored by TLC, using n-hexane/ethyl acetate as
the eluent). The solvent was diluted with 50 mL of water and the
resulting precipitate was collected by filtration. The crude
product was recrystallised with dichloromethane/n-hexane (60/
40) to give the pure solid sample for analysis.
ꢀ1
m [mm
Reflections used
]
0.10
7692
8305
6633
Independent [Rint
]
3172 (0.019)
3817 (0.022) 3241 (0.018)
Observed [I . 3s(I)] 2573
Parameters refined 192
3234
220
2756
184
Max/min Dr [e A˚ ꢀ3] 0.22/ꢀ0.22
0.19/ꢀ0.22 0.21/ꢀ0.16
1.48 1.44
0.035/0.101 0.031/0.096
1038676 1038677
GOF
2
R(F)/wR(F )
1.62
1,3-Dioxo-1-phenyl-3-(phenylamino)-2-(pyridin-1-ium-
0.039/0.111
1038675
CCDC number
1-yl)propan-2-ide (3a)
Greenish yellow crystals (95 % yield). mp 2198C; n
max
ꢀ
1
(
KBr)/cm 3444br (NH), 1639, 1619 (C¼O), 1587, 1503
(C¼C). d (400 MHz, CDCl ) 12.51 (1H, s, NH, amide),
8.52–7.01 (15H, m, Ar). d (100 MHz, CDCl ) 178.22, 163.58
carbamothioyl)-2-(4-methoxyphenyl)-2-oxo-1-(4-(pyridin-4-
ꢀ
H
3
yl)-pyridineium-1-yl)ethanide displays the Ph–C(O)–C –
C(S)–NH backbone comparable to those of 3c and 3d.
C
3
(C¼O), 149.12, 141.66, 140.46, 129.04, 128.82, 128.76, 128.43,
þ
1
27.01, 119.85. m/z 316 (5 %, [M] ), 235 (21), 196 (100), 167
Crystal Structure Determination
(19), 119 (80), 105 (30), 91 (68), 77 (62), 65 (94), 51 (50). Anal.
Calc. for C H N O : C 75.93, H 5.10, N 8.86 %. Found:
C 75.79, H 5.01, N 8.52 %.
Data were collected using Gemini Atlas CCD diffractometer
with graphite monochromated MoKa radiation (l 0.71073 A˚ )
at 120 K. The structures were solved by charge flipping
20 16 2 2
1-Methoxy-1,3-dioxo-3-(phenylamino)-2-(pyridin-1-
[
25]
2
methods and refined by full matrix least-squares on F value
[
ium-1-yl)propan-2-ide (3b)
26]
using Jana2006 suite of programs.
visualised with MCE.
Electron density was
All hydrogen atoms were discernible
[27]
Yellow crystals (93 % yield). mp 178–1818C. n
(KBr)/
max
ꢀ
1
cm 3411br (NH), 1627 (C¼O), 1580, 1520, 1482 (C¼C). d
in Fourier difference maps, but according to common practice
the hydrogen atoms connected to carbon atoms were placed in
ideal positions, while the hydrogen atoms connected to het-
eroatoms were refined with restrained geometry. In all cases
U (H) was set to 1.2U (C,N,O). All non-hydrogen atoms were
H
1
300 MHz, CDCl ) 10.62 (1H, s, N H, amide), 8.57–6.95 (10H,
(
m, C H, C H, C H, C H, C H, C H, C H, C H, C H, C H),
3
5
6
7
8
9
10
11
12
13
14
1
5
3
2
3
1
(
.62 (3H, s, C H ). d (75 MHz, CDCl ) 174.87 (C ¼O ),
3
C
3
1
1
64.14 (C ¼O ), 149.69, 141.21, 128.71, 125.69, 119.34, 50.14
iso
eq
3
15
þ
O C H ). m/z 270 (6 %, [M] ), 213(9), 178 (13), 152 (68),
3
refined using harmonic refinement. For details of the crystal-
lographic data see Table 2.
119 (100), 101 (14), 91 (94), 86 (24), 79 (24), 64 (53), 52 (30).
Anal. Calc. for C H N O : C 66.66, H 5.22, N 10.36 %.
Found: C 66.57, H 5.19, N 10.15 %.
1
5 14 2 3
Conclusions
In summary, we have described herein the reaction of hetero-
aromatic N-ylides, particularly pyridinium and isoquinolinium
ylides, with phenylisocyanate and isothiocyanates leading to the
formation of mesoionic monosubstituted 3-oxo-propanamide or
thioamide derivatives. The resulting compounds are stable at
room temperature and the solid state structures of compounds
1
-Oxo-1-phenyl-3-(phenylamino)-2-(pyridin-1-ium-1-
yl)-3-thioxopropan-2-ide (3c)
Greenish yellow crystals (90 % yield). mp 179–1808C. n
max
ꢀ1
(
(
KBr)/cm 3424br (NH), 1618 (C¼O), 1595 (C¼S), 1570
C¼C). d (300 MHz, [D6]DMSO) 14.54 (1H, s, N1H, thioa-
H
5
6
7
8
9
10
mide), 8.95–7.10 (15H, m, C H, C H, C H, C H, C H, C H,
3
b–d were established using X-ray crystallography. Prominent
11
12
13
14
16
17
C H, C H, C H, C H, C H, C H, C H, C H, C H). d
18
19
20
C
among the advantages of these reactions are novelty, operational
simplicity, and excellent yields. Further expansion of the syn-
thesis scope and biological activity of similar compounds is in
progress in our laboratory.
1
1
3
1
(
75 MHz, [D6]DMSO) 184.59 (C ¼S ), 177.81 (C ¼O ),
1
1
2
51.85, 145.61, 141.42, 141.29, 128.81, 128.61, 128.28,
26.88, 123.27. m/z 332 (6 %, [M] ), 253 (7), 251 (10),
36 (5), 196 (12), 162 (57), 135 (100), 105 (61), 91 (12), 77
þ
(
8
98), 51 (44). Anal. Calc. for C H N OS: C 72.26, H 4.85, N
20 16 2
Experimental
.43 %. Found: C 72.01, H 4.75, N 8.22 %.
-Methoxy-1-oxo-3-(phenylamino)-2-(pyridin-1-ium-1-
General Information
1
Melting points were measured on an Electrothermal-9100
apparatus and are uncorrected. IR spectra were recorded on a
1
Bruker FT-IR Tensor 27 infrared spectrophotometer. H NMR
and spectra were recorded on an Avance III 400 or 300 MHz
yl)-3-thioxopropan-2-ide (3d)
ꢀ1
Yellow crystals (93 % yield). mp 1708C. nmax (KBr)/cm
3444br (NH), 1640 (C¼O), 1592 (C¼S), 1564 (C¼C).

Pyridinium and Isoquinolinium Ylides
E
1
d (300 MHz, CDCl ) 11.83 (1H, s, N H, thioamide), 8.61–7.09
C H N OS: C 75.37, H 4.74, N 7.32 %. Found: C 75.14,
24 18 2
H
3
5
6
7
8
9
10
11
12
13
10H, m, C H, C H, C H, C H, C H, C H, C H, C H, C H,
(
C H), 3.59 (3H, s, C H ). d (75 MHz, CDCl ) 182.87
H 4.55, N 7.01 %.
1
4
15
3
C
3
1
1
3
1
(
1
C ¼S ), 162.79 (C ¼O ), 151.30, 143.47, 128.26, 126.23,
2-(Isoquinolin-2-ium-2-yl)-1-methoxy-1,3-dioxo-3-
(phenylamino)propan-2-ide (5c)
2
09.67, 50.49 (O C H ). m/z 286 (4 %, [M] ), 260 (6), 234
15
þ
3
(
1
12), 207 (7), 205 (13), 191 (12), 176 (13), 135 (100), 119 (32),
04 (11), 91 (28), 77 (87), 64 (18), 51 (58). Anal. Calc. for
C H N O S: C 62.92, H 4.93, N 9.78 %. Found: C 62.75,
ꢀ1
Orange crystals (93 % yield). mp 1358C. nmax (KBr)/cm
3
443br (NH), 1638, 1617 (C¼O), 1581, 1526 (C¼C). d
H
1
5
14
2
2
(300 MHz, CDCl ) 10.72 (1H, s, NH), 9.28 (1H, s, HC ¼N),
3 C
3
a
.30–6.94 (11H, m, Ar), 3.65 (3H, s, OCH ). d (75 MHz,
H 4.85, N 9.67 %.
8
CDCl ) 177.53, 164.46 (C¼O), 152.88, 141.04, 140.47,
3
1
-(Methylamino)-3-oxo-3-phenyl-2-(pyridin-1-ium-1-
136.13, 135.53, 130.16, 129.75, 128.72, 127.48, 126.74,
123.31, 121.72, 119.39, 98.20, 50.19 (OCH ). m/z 320 (9 %,
yl)-1-thioxopropan-2-ide (3e)
3
þ
[
M] ), 260 (8), 228 (19), 201 (87), 170 (17), 143 (100), 130 (59),
Russet brown crystals (90 % yield). mp 958C. n
(KBr)/
max
ꢀ
1
119 (86), 102 (18), 91 (64), 77 (26), 64 (40), 51 (26). Anal. Calc.
for C H N O : C 71.24, H 5.03, N 8.74 %. Found: C 70.94,
H 4.88, N 8.46 %.
cm 3493 (NH), 1639 (C¼O), 1619 (C¼N). d (400 MHz,
H
3
D6]DMSO) 12.16 (1H, q, J
3
4, NH), 8.83 (2H, d, J
[
H -py), 8.32 (1H, t, J
8,
8,
19 16 2 3
H–H
H–H
3
3
8, H -py), 7.79 (2H, t, J
a
H -py), 7.12–7.08 (5H, m, Ar), 3.10 (3H, d, J
H–H
g
H–H
3
4, CH ). dC
3
b
H–H
Crystallographic Data
(
(
(
100 MHz, [D6]DMSO) 183.34 (C¼S), 163.83 (C¼O), 151.29
C¼N), 144.67, 141.49, 127.75, 127.68, 126.15, 126.06, 112.02
CCDC 1038675–1038677 contain the supplementary crystallo-
graphic data for compounds 3b, 3c, and 3d respectively. These
data can be obtained free of charge via http://www.ccdc.cam.
ac.uk/conts/retrieving.html or from the Cambridge Crystallo-
graphic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK;
fax: þ44 1223 336 033; or email: deposit@ccdc.cam.ac.uk.
ꢀ
þ
C ), 31.16 (NCH ). m/z 270 (35 %, [M] ), 269 (14), 237 (16),
3
191 (21), 163 (8), 118 (15), 105 (100), 77 (85), 51 (43). Anal.
Calc. for C H N OS: C 66.64, H 5.22, N 10.36 %. Found:
C 66.48, H 5.04, N 10.09 %.
1
5 14 2
1-Methoxy-3-(methylamino)-1-oxo-2-(pyridin-1-ium-1-
yl)-3-thioxopropan-2-ide (3f)
Supplementary Material
ꢀ
1
1
13
Yellow crystals (90 %). mp 174–1758C. nmax (KBr)/cm
IR, H, C NMR, and mass spectral data for a representative set
of compounds 3a–f and 5a–d are available on the Journal’s
website.
3
DMSO) 9.70 (1H, q, J
493 (NH), 1695 (C¼O), 1632 (C¼N). d (300 MHz, [D6]
H
3
3
6, NH), 8.74 (2H, d, J
6, H -py),
H–H
H–H a
3
.47 (1H, t, J
3
6, H -py), 7.96 (2H, t, J
8
(
6, H -py), 3.39
H–H b
H–H
g
3
3H, s, OCH ), 3.02 (3H, d, J
6, NCH ). d (75 MHz, [D6]
3
Acknowledgements
3
H–H
C
DMSO) 185.71 (C¼S), 164.14 (C¼O), 151.91 (C¼N), 144.96,
The authors express appreciation to the Shahid Bahonar University of
Kerman Faculty Research Committee for its support of this investigation.
The Chemistry Department, University of Otago, is thanked for the con-
tinued support of the work of JS. Crystallographic work was also supported
by Project 15–12653S of the Czech Science Foundation.
ꢀ
1
27.15, 107.45 (C ), 50.11 (OCH ), 31.51 (NCH ). m/z 224
3
3
þ
(
100 %, [M] ), 223 (66), 191 (49), 164 (13), 113 (11), 93 (10),
8
N 12.49 %. Found: C 51.08, H 5.19, N 12.22 %.
0 (93), 52 (34). Anal. Calc. for C H N O S: C 53.55, H 5.39,
1
0 12 2 2
References
2
(
-(Isoquinolin-2-ium-2-yl)-1,3-dioxo-1-phenyl-3-
phenylamino)propan-2-ide (5a)
Orange crystals (96 % yield). mp 191–1938C. nmax (KBr)/
[1] D. W. Ollis, S. P. Stanforth, Tetrahedron 1985, 41, 2239. doi:10.1016/
S0040-4020(01)96625-6
[
2] Y. Karzazi, G. Surpateanu, Heterocycles 1999, 51, 863. doi:10.3987/
ꢀ
1
cm 3411br (NH), 1632, 1590 (C¼O), 1536, 1501 (C¼C). d
H
REV-98-507
[3] A. Padwa, 1,3-Dipolar Cycloaddition Chemistry 1984 (Wiley:
(
8
300 MHz, CDCl ) 12.57 (1H, s, NH), 9.20 (1H, s, HC ¼N),
3
a
.19–6.99 (16H, m, Ar). d (75 MHz, CDCl ) 178.52, 164.03
C 3
New York, NY).
(
C¼O), 152.21, 140.65, 140.47, 140.03, 136.01, 130.55, 129.65,
[4] M. Zahedifar, H. Sheibani, Aust. J. Chem. 2014, 67, 1201. doi:10.1071/
CH14095
[5] M. Abaszadeh, H. Sheibani, K. Saidi, Aust. J. Chem. 2010, 63, 92.
doi:10.1071/CH09344
1
1
2
7
7
28.78, 128.73, 128.37, 127.16, 127.02, 126.82, 123.37, 122.43,
20.07, 119.06, 116.06. m/z 366 (2 %, [M] ), 363 (59), 347 (8),
þ
47 (41), 204 (12), 144 (10), 129 (60), 105 (100), 91 (10),
7 (93), 51 (35). Anal. Calc. for C H N O : C 78.67, H 4.95, N
.65 %. Found: C 78.49, H 4.80, N 7.37 %.
[
[
[
[
6] H. Sheibani, P. V. Bernhardt, C. Wentrup, J. Org. Chem. 2005, 70,
2
4 18 2 2
5
859. doi:10.1021/JO050428M
7] F. Dumitrascu, M. T. Caproiu, F. Georgescu, B. Draghici, M. M. Popa,
E. Georgescu, Synlett 2010, 2407. doi:10.1055/S-0030-1258035
8] P. Woisel, G. Surpateanu, F. Delatre, M. Eur Bria, Eur. J. Org. Chem.
2
-(Isoquinolin-2-ium-2-yl)-1-oxo-1-phenyl-3-
phenylamino)-3-thioxopropan-2-ide (5b)
Brown crystals (95 % yield). mp 149–1518C. nmax
(
2
001, 7, 1407.
9] A. Rotaru, I. Druta, T. Oeser, T. J. J. Muller, Helv. Chim. Acta 2005, 88,
ꢀ1
1798. doi:10.1002/HLCA.200590141
10] D. S. Allg a¨ uer, H. Mayer, H. Mayer, J. Am. Chem. Soc. 2013, 135,
(
KBr)/cm 3444br (NH), 1635 (C¼O), 1619, 1597 (C¼C).
[
[
[
dH (300 MHz, [D6]DMSO) 14.61 (1H, s, NH), 10.09 (1H, s,
HC ¼N), 8.58–6.80 (16H, m, Ar). d (75 MHz, [D6]DMSO)
1
5216. doi:10.1021/JA407885H
a
C
11] L. R. Falvello, S. Fern a´ ndez, R. Navarro, E. P. Urriolabeitia, Inorg.
Chem. 1997, 36, 1136. doi:10.1021/IC960904E
12] R. Postolachi, R. Danac, N. J. Buurma, A. Pui, M. Balan, S. Shova,
1
1
1
3
1
84.80 (C¼S), 178.14 (C¼O), 156.64, 142.14, 141.53, 141.36,
37.28, 137.02, 130.93, 130.66, 129.94, 129.31, 128.83,
28.61, 128.24, 127.37, 127.24, 126.62, 124.05, 123.33. m/z
C. Deleanu, RSC Adv. 2013, 3, 17260. doi:10.1039/C3RA41911H
[13] S. Danishefsky, Acc. Chem. Res. 1979, 12, 66. doi:10.1021/
þ
82 (5 %, [M] ), 380 (18), 362 (12), 351 (17), 298 (13), 241 (9),
29 (15), 105 (100), 77 (94), 51 (23). Anal. Calc. for
AR50134A004

F
M. Seifi et al.
[
[
[
[
[
[
[
[
14] D. M. Jerina, J. M. Daly, Science 1974, 185, 573. doi:10.1126/
[22] Y. G. Gololobov, O. V. Dovgan, I. R. Golding, P. V. Petrovskii,
I. A. Garbuzova, Heteroat. Chem. 2002, 13, 36. doi:10.1002/
HC.1104
[23] J. Bernstein, R. E. Davis, L. Shimoni, N.-L. Chang, Angew. Chem., Int.
Ed. Engl. 1995, 34, 1555. doi:10.1002/ANIE.199515551
[24] C. R. Groom, F. H. Allen, Angew. Chem. Int. Ed. 2014, 53, 662.
doi:10.1002/ANIE.201306438
[25] L. Palatinus, G. Chapuis, J. Appl. Cryst. 2007, 40, 786. doi:10.1107/
S0021889807029238
[26] V. Petricek, M. Dusek, L. Palatinus, Z. Kristallogr. 2014, 229, 345.
[27] J. Rohlicek, M. Husak, J. Appl. Cryst. 2007, 40, 600. doi:10.1107/
S0021889807018894
SCIENCE.185.4151.573
15] G. Surpateanu, J. P. Catteau, P. Karafiloglou, A. Lablache-Combier,
Tetrahedron 1976, 32, 2647. doi:10.1016/0040-4020(76)80103-2
16] C. D. Papageorgiou, M. A. Cubillo de Dios, S. V. Ley, M. J. Gaunt,
Angew. Chem. Int. Ed. 2004, 43, 4641. doi:10.1002/ANIE.200460234
17] S. Kojima, K. Fujitomo, Y. Shinohara, M. Shimizu, K. Ohkata, Tetra-
hedron Lett. 2000, 41, 9847. doi:10.1016/S0040-4039(00)01743-3
18] S. Kojima, M. Suzuki, A. Watanabe, K. Ohkata, Tetrahedron Lett.
2
006, 47, 9061. doi:10.1016/J.TETLET.2006.10.085
19] A. Domling, I. Ugi, Angew. Chem. Int. Ed. 2000, 39, 3168. doi:10.1002/
521-3773(20000915)39:18,3168::AID-ANIE3168.3.0.CO;2-U
1
20] C. G. Yan, X. M. Cai, Q. F. Wang, T. Y. Wang, M. Zheng, Org.
Biomol. Chem. 2007, 5, 945. doi:10.1039/B617256C
21] Y. Han, H. Hou, Q. Fu, C. G. Yan, Tetrahedron 2011, 67, 2313.
doi:10.1016/J.TET.2011.01.046
[28] A. Hazra, S. Mondal, A. Maity, S. Naskar, P. Saha, R. Paira,
K. B. Sahu, P. Paira, S. Ghosh, C. Sinha, A. Samanta, S. Banerjee,
N. B. Mondal, Eur. J. Med. Chem. 2011, 46, 2132. doi:10.1016/
J.EJMECH.2011.02.066