Sodium persulfate-promoted site-selective synthesis of mononitroarylamines under transition-metal-free conditions

Article abstract of DOI:10.1016/j.tet.2019.01.011

A practical preparation of nitroarylamines from protected arylamines was herein disclosed. In this system, sodium nitrite acted as a nitration reagent in the presence of sodium persulfate without any transition-metal catalysts. This efficient site-selective protocol took place at room temperature for a short time through a free radical pathway.

Full text of DOI:10.1016/j.tet.2019.01.011

Accepted Manuscript
Sodium persulfate-promoted site-selective synthesis of mononitroarylamines under
transition-metal-free conditions
De-Xun Xie, Hui-Juan Yu, Hui Liu, Wei-Cai Xue, Yuan-Shou Qin, Guang Shao
PII:
S0040-4020(19)30026-2
https://doi.org/10.1016/j.tet.2019.01.011
TET 30063
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 15 September 2018
Revised Date: 28 December 2018
Accepted Date: 7 January 2019
Please cite this article as: Xie D-X, Yu H-J, Liu H, Xue W-C, Qin Y-S, Shao G, Sodium persulfate-
promoted site-selective synthesis of mononitroarylamines under transition-metal-free conditions,
Tetrahedron (2019), doi: https://doi.org/10.1016/j.tet.2019.01.011.
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Sodium Persulfate-Promoted Site-Selective Synthesis
of Mononitroarylamines under Transition-Metal-Free
Conditions
†
†
† †
† †
† ††
†
De-Xun Xie, Hui-Juan Yu, Hui Liu, Wei-Cai Xue , Yuan-Shou Qin and Guang Shao*
†
School of Chemistry, Sun Yat-sen University, Guangzhou, 510275, PR China; Shenzhen Research Institute, Sun
Yat-sen University, Shenzhen, 518057, PR China; South China Advanced Materials Science & Technology
(
Guangzhou) Co., Ltd, Guangzhou, 511400, P. R. China
†
†
Aneo Chem-Tech Co., Ltd, Guangzhou, 510670, P. R. China
†
††
Zeloq (Shenzhen) Technology Co. Ltd., Shenzhen, 518104, P. R. China
Email: shaog@mail.sysu.edu.cn
A site-selective preparation of nitroarylamines was herein disclosed from protected arylamines and sodium
nitrite in the presence of Na S O without any transition-metal-catalysts. The mild protocol took place at room
2
2
8
temperature for a short time through a free radical mechanism with broad substrate scope and high efficiency.

1
ACCEPTED MANUSCRIPT
Tetrahedron
journal homepage: www.elsevier.com
Sodium
Persulfate-Promoted
Site-Selective
Synthesis
of
Mononitroarylamines under Transition-Metal-Free Conditions
†
†
† †
† †
† ††
†
De-Xun Xie, Hui-Juan Yu, Hui Liu, Wei-Cai Xue , Yuan-Shou Qin and Guang Shao*
†
School of Chemistry, Sun Yat-sen University, Guangzhou, 510275, PR China; Shenzhen Research Institute, Sun Yat-
sen University, Shenzhen, 518057, PR China; South China Advanced Materials Science & Technology (Guangzhou)
Co., Ltd, Guangzhou, 511400, P. R. China.
†
†
†
Aneo Chem-Tech Co., Ltd, Guangzhou, 510670, P. R. China
Zeloq (Shenzhen) Technology Co. Ltd., Shenzhen, 518104, P. R. China
††
Email:shaog@mail.sysu.edu.cn
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
A practical preparation of nitroarylamines from protected arylamines was herein disclosed. In
this system, sodium nitrite acted as a nitration reagent in the presence of sodium persulfate
without any transition-metal catalysts. This efficient site-selective protocol took place at room
temperature for a short time through a free radical pathway.
Available online
2009 Elsevier Ltd. All rights reserved.
Keywords:
Transition-metal-free
Sodium nitrite
Sodium persulfate
Site-selective
Mononitroarylamines
1
. Introduction
Site-selectivity and benign conditions (transition-metal-free,
green solvent or even solvent-free) have become joint concerns
from the communities of methodology and green chemistry
research. Within this context, we would like to disclose a sodium
persulfate-promoted nitration of protected arylamines with
sodium nitrite for a short time (ca. 1 hour) but without any
transition-metal catalysts, with high efficiency and good site-
selectivity (C2-nitration for anilines, and C4-nitration for 2-
naphthylamines).
Nitroarylamines have drawn widespread research interests for
their broad applications in the fields of pharmaceutical, plastic,
natural products and dyes, as well as the key synthetic
intermediates in the community of chemical industry. Therefore,
continuous efforts have been sacrificed for the installation of
nitro group, and fruitful achievements have been witnessed on
the topic. It is universally acknowledged that traditional
methodologies, with HNO /H SO
halides, aryl boronic acids , aryl amines, aryl azides and
others, suffered from the harsh conditions, poor regioselectivity,
limited substrate scope and atom/step-economic issues. Thus,
appealing ortho- and meta-nitration through the chelation-
[
1]
[
2]
[
3]
or ipso-nitration of aryl
3
2
4
[
4]
[5]
[6] [7]
2. Results and discussions
[
8]
The studies began with the reactions between N-phenyl 2-
pyridinecarboxamide (1a) and sodium nitrite (NaNO ) to gain the
2
2
assisted C(sp )-H bond activation pathway were established by
using Cu(NO ) , AgNO3,
the nitro suppliers, occasionally with the assistance of expensive
Pd, Ru Rh and Co salts as the catalysts. Demonstrated
optimal conditions, which are shown in Table 1. Surprisingly, in
[
9]
[9b,10]
[11]
[12]
3
2
and Fe(NO3)3,
and so on as
the presence of Cu(OAc) as the catalyst and pivalic acid (PivOH)
2
as the additive, the effects of different organic peroxide oxidants
varied sharply in the transformation. For example, di-tert-butyl
peroxide (DTBP) rendered the occurrence of the C-N coupling
reaction in 58% yield, while tert-butyl hydroperoxide (TBHP)
and dicumyl peroxide (DCP) afforded only trace 2a in 1,2-
dichloroethane (DCE) at room temperature for 1 hour (entries 1 -
[
13]
[14]
[15]
[16]
[
17a]
[17b]
by Arns
and Hajra,
nitrated arylamines were successfully
synthesized from protected amines (amides) with highly active
tert-butyl nitrite (TBN) in acetonitrile under mild conditions,
without any transition-metal catalysts, which ruled out the metal
contamination of products. Sodium nitrite, previously applied as
3
). The addition of 2,3-dicyano-5,6-dichloro-benzoquinone
(DDQ) failed to offer the desired product 2a within 1 hour (entry
). To our satisfactory, organic hypervalent iodine-reagents, like
an efficient NO donator in the presence of different transition-
2
metal catalysts, possesses the advantages like low cost/toxicity,
high stability and none-explosive property. Very recently, König
reported a visible light and organic photocatalyst-mediating
nitration reaction at room temperature in
MeCN/H O towards mono- and di-nitroanilines in good yields.
4
Dess-Martin periodinane (DMP for entry 5), phenyliodonium
diacetate (PIDA for entry 6) and phenyliodonium
bis(trifluoroacetate) (PIFA for entry 7) made the nitration
reaction occure in acceptable yields (from 10% to 78%), but
a mixture of
[18]
2

2
Tetrahedron
o
inferior to the performance of sodium persul
A
fat
C
e
C
did
E
(
P
82
T
%
E
f
D
or MA
C
NU
) w
to an easy formation of 2c in the presence of NaNO and Na S O
8
a
S
s p
C
ro
R
ve
I
d crucial to nitration of the substrate 1c, which led
P
T
entry 8). However, H O failed to make the oxidative reaction
2
2
2
2
2
happen (entry 9). The absence of PivOH offered a higher 70%
yield of 2a under the ambient conditions (entry 10). Successively,
the activities of various Cu(II) and Cu(I)-catalysts were also
examined in the system. However, beyond our expectations, all
the transition-metal catalysts gave positive effect and the desired
nitrated product 2a was successfully furnished in yields ranging
from 80% to 83% (entries 11 - 15). Based on the findings, the
role of the Cu(II) or Cu(I)-catalysts was suspected. The
investigation was then continued in the absence of the catalysts,
and an exciting 83% yield of 2a was successfully isolated under
the transition-metal-free conditions with the assistance of
Na S O in DCE at room temperature for 1 hour (entry 16). Other
(footnote b). Worthy of note, 2d and 2e were detected as the
exclusive products under the mild conditions, and the nitration
took place on the specific ortho-positions of the substrates
probably due to the steric factors. The substrates decorated with
other alkyl groups were also compatible in the system, and N-(2-
nitro-4-ethylphenyl)-,
N-(2-nitro-4-tert-butylphenyl)
2-
pyridinecarboxamides (2f and 2g) were smoothly provided in
70% and 81% yields, respectively. Substrate bearing electron-
sufficient phenyl group gave better performance, which was
exemplified by the formation of N-(2-nitro-4-methoxyphenyl) 2-
pyridinecarboxamides (2h) in the highest 90% yield.
Successively, compatibilities of the halo groups were also
checked under the mild conditions. N-(4-fluorophenyl)-, N-(4-
chlorophenyl)-, N-(4-bromophenyl)- and N-(4-iodophenyl) 2-
pyridinecarboxamides (1i – 1l) furnished the corresponding nitro
substituted products 2i – 2l in yields from 68% to 79%.
Substrates with electron-deficient phenyl groups generally
offered inferior efficiency in the transformation. For example, 4-
[(2-pyridinylcarbonyl)amino] benzoic ethyl ester (1m) was
nitrated at room temperature for 1 hour, yielding the nitro
product 2m in a 60% ratio. The nitration of N-(4-trifluorophenyl)
2
2
8
organic solvents, including MeCN, N,N-dimethyl formamide
DMF), dimethyl sulfoxide (DMSO), 1,4-dioxane, PEG-400
(
showed performance inferior to DCE did in the system, for lower
yields or even trace of 2a was observed in the transformation
(entries 17 - 21). No product was detected in the absence of the
oxidant Na S O in DCE at room temperature for 1 hour (entry
2
2
8
2
2).
Table 1. Optimization of The Reaction Conditions
2
-pyridinecarboxamide (1n) did not readily take place at room
temperature, however, forming 2n in 62% yield at an elevated
temperature (footnote b). But in comparison, N-(4-cyanophenyl)
2
-pyridinecarboxamide (1o) refused to undergo the nitration
reaction under the standard conditions.
b
Entry
Cat.
Additive
[O]
Sol.
DCE
Yield
58%
a
Table 2. Scope of N-Aryl 2-Pyridinecarboxamides
1
2
3
4
5
6
7
8
9
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
2
2
2
2
2
2
2
2
2
2
PivOH
DTBP
TBHP
DCP
PivOH
DCE
trace
trace
n.d.
PivOH
DCE
PivOH
DDQ
DMP
PIDA
PIFA
DCE
PivOH
DCE
10%
60%
78%
82%
n.d.
PivOH
DCE
PivOH
DCE
PivOH
2 2
Na S O
8
DCE
PivOH
2
H O
2
DCE
10
11
12
13
14
15
16
17
18
19
20
21
22
--
--
--
--
--
--
--
--
--
--
--
--
--
Na
Na
Na
Na
Na
Na
Na
Na
Na
Na
Na
Na
2 2
S O
2 2
S O
2 2
S O
2 2
S O
2 2
S O
2 2
S O
2 2
S O
2 2
S O
2 2
S O
2 2
S O
2 2
S O
2 2
S O
8
8
8
8
8
8
8
8
8
8
8
8
DCE
70%
83%
82%
82%
83%
80%
83%
58%
Trace
Trace
62%
55%
n.d.
CuCl
2
DCE
CuBr
2
DCE
CuCl
CuBr
CuI
--
DCE
DCE
DCE
DCE
--
MeCN
DMF
DMSO
Dioxane
PEG-400
DCE
--
--
--
--
--
--
a
2
Conditions: 1a (0.3 mmol), NaNO (0.36 mmol), Cat. (10 mol%),
additive (20 mol%), [O] (0.6 mmol), sol. (1.5 mL) at r.t. for 1 h.
b
Isolated yields.
With the optimal conditions successfully established, the scope
and limits of different N-aryl 2-pyridinecarboxamides were
evaluated under the transition-metal-free conditions, as shown in
table 2. Gratifyingly, the substrates with methyl group were all
well-tolerated in the system, and nitro groups were successfully
installed on the substrates. For instance, N-(p-tolyl)-, N-(o-tolyl)-,
N-(m-tolyl)- and N-(3,4-dimethylphenyl) 2-pyridinecarboxamides
a
Conditions:
2 2 2 8
1 (0.5 mmol), NaNO (0.6 mmol), Na S O (2.0 equiv.) at r.t.
b
(1b – 1e) afforded the corresponding nitrated products 2b – 2e in
in DCE (2.5 mL) for 1 hour and isolated yields otherwise noted. The
yield was obtained at 60 C.
o
yields from 68% to 78%. However, an elevated temperature (60

3
In the same pattern, the reactivity of substra
protecting groups was evaluated under the transition-metal-free
conditions (Table 3).
A
tes
C
w
C
it
E
h
P
di
T
ff
E
ere
D
nt MAto
N
lyl
U
) b
S
en
C
za
R
m
I
ide (1u) under the standard conditions, providing
P
T
2u in a medium 70% yield. In contrast, N-Boc and N-pivaloyl
protected amides (1v and 1w) refused to undertake the nitration
reaction for the desired products (2v and 2w). Surprisingly, N-(p-
tolyl) P,P-diphenyl phosphinamide (1x) and N-(p-tolyl) P-
methoxy-P-phenyl phosphonamide (1y), which were known for
fragile P-N bond, underwent the nitration reaction smoothly,
affording the corresponding nitro-bearing products 2x and 2y in
acceptable 48% and 42% yields, respectively. Furthermore,
reactions for the nitration of naphthyl groups, which was assisted
by various protecting groups, were also conducted under the mild
conditions in a site-selective manner. However, C4 position on
the naphthyl-ring (α-position), who possessed a higher reactivity,
other than C2-site (β-position) enjoyed the superiority for the
installation of the nitro group in the system. Thus, N-(1-naphthyl)
a
Table 3. Substrate Scope of Protected Arylamines
2
-pyridinylcarboxamide (1z), N-(1-naphthyl) 3-methyl-2-
pyridinylcarboxamide (1a'), N-(1-naphthyl) 6-methyl-2-
pyridinylcarboxamide (1b') and N-(1-naphthyl) 3-fluoro-2-
pyridinylcarboxamide (1c') efficiently furnished the
corresponding nitro-decorated products 2z and 2a' - 2c' at C4-
position in yields from 48% to 76%. The substrates with different
protecting
quinolinylcarboxamide
groups,
such
(1d'),
as
N-(1-naphthyl)
N-(1-naphthyl)
2-
2-
thiophenylcarboxamide (1e') and N-(1-naphthyl) benzamide (1f’),
were successfully nitrated on the specific positions, yielding the
corresponding 2d' – 2f' in ratios from 52% to 80%. N-(2-methyl-
4
-nitro-1-naphthyl)-
and
N-(1-nitro-2-naphthyl)
2-
pyridinylcarboxamide (2g' and 2h') were isolated as the
exclusive product from the mild system in 42% and 58% yields,
respectively.
To illustrate the potential for industrial production of the useful
nitration compounds, the scale-up reaction was carried out under
the mild conditions as shown in Scheme 1 (Eq. A). 1.141 g 1h
(
ca. 5.0 mmol) was successfully nitrated in DCE at room
temperature, furnishing 1.091 g of the desired product 2h in ca.
0% yield, slightly lower than in 0.5 mmol scale (90%, Table 2).
8
To explore the application of the practical and facile
transformation, deprotection reactions were conducted on the
nitro-installed molecules 2h, 2k (C2-nitration products) and 2z
(
C4-nitration product). By treatment with NaOH (6.0 equivalents)
o
in ethanol at 90 C for 8 hours, 2-nitro-4-methoxy aniline (3a), 2-
nitro-4-bromo aniline (3b) and 4-nitro-1-naphthylamine (3c)
were successfully afforded in high yields (Eq. B and C), which
were difficult to prepare by traditional means.
a
Conditions:
2 2 2 8
1 (0.5 mmol), NaNO (1.0 mmol), Na S O (2.0 equiv.) in DCE
(2.5 mL) at r.t. for 1 hour in noted isolated yields.
N-(4-tolyl) 3-methyl-2-pyridinecarboxamide (1p) and N-(4-tolyl)
-methyl-2-pyridinecarboxamide (1q) were smoothly nitrated by
6
NaNO2 at room temperature for 1 hour, leading to the
corresponding products 2p and 2q in 68% and 58% yields,
respectively. The fluorinated pyridine-protecting substrates, as
illustrated by the nitration of N-(4-tolyl) 3-fluoro-2-
pyridinecarboxamide (1r), failed to undergo the transformation,
which might be due to the electron-factors. Next, the heterocyclic
protecting groups, such as N-(4-tolyl) 2-quinolinylcarboxamide
Scheme 1. Scale-up and Deprotection Reactions
(1s) and N-(4-tolyl) 2-thiophenylcarboxamide (1t), were also
subjected to the transition-metal-free conditions and allowed the
formation of nitro products in 72% and 48% yields, respectively.
To our satisfactory, the nitro group could be installed on N-(4-
The radical scavenger 2,2,6,6-tetramethyl piperidine-1-oxyl
(TEMPO) was added to take a deeper insight into the

4
Tetrahedron
on MAIn
-
mechanism of this protocol, which depress
A
ed
C
th
C
e
E
fo
P
rm
T
a
E
ti
D
N
fra
U
redSC(IR
R
)
IP
s ctra were reported in reciprocal centimeter (cm
pe
). Melting points were recorded on a national standard melting
point apparatus (Model: Taike XT-4) and uncorrected.
T
1
of the desired product significantly and only a trace of
product was observed by TLC (thin layer chromatography)
analysis. Based on the findings and previous reports,
radical mechanism of the mild reaction was herein proposed
as exemplified with the formation of 2a (Scheme 2).
Initially, sodium nitrite interacted with sodium persulfate,
[
17,18]
a
4
.2 General Procedure
4
.2.1 Procedures towards N-aryl Phosphonic/Phosphinic Amides
N-Aryl protected carboxamide (1, 0.5 mmol, 1.0 equiv.), NaNO2
0.6 mmol, 1.2 equiv.) were transferred to DCE (2.5 mL) and
then Na S O (1.0 mmol, 2.0 equiv.) were added to the mixture in
affording the NO radicals in the system. 1a gave an easy
2
(
access to a free radical intermediate
sodium persulfate, which was reversibly transformed into
another two intermediates and of significant importance
but different structures. The intermediate enjoyed the
priority for further transformation because the ortho-carbon
was stabilized by the C=O group, while the intermediate
was unfavorable for further nitration on the para-position.
Thus, 2a was successfully isolated as the exclusive product
but para-nitration product 2a'' was not detected in the
protocol.
A in the presence of
2
2
8
one portion and the corresponding mixture was stirred for
additional 1 hour upon the completion of the reaction (monitored
by TLC). The crude product was washed with DCM (3 x 20 mL)
and combined. Then the organic solvent was removed by
evaporation and the residue was purified by silica gel column
chromatography with a mixture of n-hexane, dichloromethane or
ethyl acetate to afford the desired product in noted yields.
B
C
C
B
4
.2.2 N-(2-Nitrophenyl) 2-pyridinecarboxamide (2a)
S2O82-
NaNO2
NO2
Follow the general procedure, 2a was obtained as yellow solid
with n-hexane/dichlormethane (10/1) used as eluent in 78% yield
(92.3 mg). Melting point: 148 - 149 C. H NMR (400 MHz,
H
o
1
N
Py
S2O82-
N
Py
N
Py
N
Py
CDCl ) δ = 12.80 (s, 1H), 9.09 (d, J = 8.4 Hz, 1H), 8.79 (br.s,
O
O
O
O
3
1
7
H), 8.33 (t, J = 6.9 Hz, 2H), 7.98 (t, J = 7.6 Hz, 1H), 7.76 (t, J =
1a
A
B
C
unfavorable
favorable
13
.7 Hz, 1H), 7.58 (br,s, 1H), 7.33 – 7.27 (m, 1H) (ppm).
C
NMR (100 MHz, CDCl ) δ = 163.6, 149.5, 148.8, 137.8, 137.2,
3
NO2
1
35.9, 134.7, 127.1, 126.1, 123.5, 122.9, 122.2 (ppm). MS (ESI):
+
m/z (%) = 78 (65), 79 (43), 106 (47), 243.0 (90, M ). IR (in KBr):
ν = 3550, 3475, 3415, 3136, 1615, 1401, 619 (cm ). HRMS
-
1
H
N
H
N
Py
Py
+
(ESI) (m/z) [C H N O +H ]: Calcd. 244.0717, Found. 244.0719.
12 9 3 3
O
O
NO2
O2N
2
a'' (not detected)
2a (exclusive product)
4.2.3 N-(2-Nitro-4-methylphenyl) 2-pyridinecarboxamide (2b)
Follow the general procedure, 2b was obtained as yellow solid
with n-hexane/dichlormethane (10/1) used as eluent in 78% yield
Scheme 2. A Proposed Free Radical Mechanism
o
1
(100.2 mg). Melting point: 183 - 184 C. H NMR (400 MHz,
CDCl ) δ = 12.64 (s, 1H), 8.90 (d, J = 8.5 Hz, 1H), 8.73 (d, J =
3
4
7
.2 Hz, 1H), 8.28 (d, J = 7.7 Hz, 1H), 8.07 (s, 1H), 7.92 (t, J =
13
3
. Conclusion
.7 Hz, 1H), 7.51 (d, J = 8.0 Hz, 2H), 2.42 (s, 3H) (ppm).
C
NMR (100 MHz, CDCl ) δ = 163.5, 149.6, 148.8, 137.7, 137.1,
3
A
green and practical site-selective preparation of
1
36.7, 133.8, 132.3, 127.0, 125.9, 122.8, 122.2, 20.8 (ppm). MS
nitroarylamines was disclosed in the presence of sodium
persulfate without transition-metal catalysts under mild
conditions. The efficient and compatible transformation was
proved to take place through a free radical pathway at room
temperature, providing a bright avenue towards the compounds
of great significance.
+
(ESI): m/z (%) = 78 (75), 79 (43), 106 (47), 257.0 (100, M ). IR
(
in KBr): ν = 3551, 3473, 3415, 3232, 3136, 1615, 1401, 619
-1
+
(cm ). HRMS (ESI) (m/z) [C H N O +H ]: Calcd. 258.0873,
13 11 3 3
Found. 258.0881.
4
.2.4 N-(2-Nitro-6-methylphenyl) 2-pyridinecarboxamide (2c)
4
. Experimental section
Follow the general procedure, 2c was obtained as yellow
solid with n-hexane/dichlormethane (10/1) used as eluent in 72%
yield (92.5 mg). Melting point: 194 – 195 C. H NMR (400
4
.1 General remarks
o
1
All the reagents were purchased from commercial companies
1
13
and used without further purification. H and C NMR spectra
were recorded on a Varian INOVA-400 spectrometer in
deuterated chloroform at 25 °C with residue solvent peaks as
MHz, CDCl ) δ = 10.48 (s, 1H), 8.76 – 8.58 (m, 2H), 8.30 (d, J =
3
7
1
.2 Hz, 1H), 8.21 – 8.05 (m, 2H), 7.95 (t, J = 6.3 Hz, 1H), 7.54 (s,
13
H), 2.52 (s, 3H) (ppm). C NMR (100 MHz, CDCl ) δ = 162.3,
3
1
149.3, 148.4, 143.3, 142.1, 138.1, 127.6, 127.2, 125.8, 123.2,
internal standards (δ = 7.26 ppm for H-NMR and δ = 77.16 ppm
1
3
7
22.8, 119.6, 17.9 (ppm). IR (in KBr): ν = 3551, 3473, 3413,
13
for C-NMR). Chemical shifts (δ) are reported in ppm, and spin-
spin coupling constants (J) are given in Hz, while multiplicities
are abbreviated by s (singlet), d (doublet), t (triplet), q (quartet)
-1
232, 3136, 1615, 1401, 620 (cm ). MS (ESI): m/z (%) = 78 (83),
+
9 (45), 106 (50), 257.0 (100, M ). HRMS (ESI) (m/z)
+
[C H N O +H ]: Calcd. 258.0873, Found. 258.0881.
13
11
3
3
and
m (multiplet). Mass spectra were recorded on a
ThermoFinnigan MAT95XP microspectrometer and high
resolution mass spectra (HRMS) were recorded on an Agilent
Technologies Accurate Mass Q-TOF 6530 microspectrometer.
4.2.5 N-(2-Nitro-3-methylphenyl) 2-pyridinecarboxamide (2d)

5
Follow the general procedure, 2d was o
A
bta
C
in
C
ed
E
a
P
s
T
ye
E
llo
D
w
MANUFo
S
ll
C
ow
R
t
I
h
P
e
T
general procedure, 2h was obtained as yellow
solid with n-hexane/dichlormethane (10/1) used as eluent in 70%
solid with n-hexane/dichlormethane (10/1) used as eluent in 90%
yield (122.9 mg). Melting point: 192 – 193 C. H NMR (400
o
1
o
1
yield (89.9 mg). Melting point: 123 – 124 C. H NMR (400
MHz, CDCl ) δ = 10.27 (s, 1H), 8.63 (d, J = 3.5 Hz, 1H), 8.30 (d,
MHz, CDCl ) δ = 12.53 (s, 1H), 8.93 (d, J = 9.3 Hz, 1H), 8.73 (d,
3
3
J = 7.8 Hz, 1H), 8.12 (d, J = 8.8 Hz, 1H), 7.95 (t, J = 7.6 Hz, 1H),
J = 3.8 Hz, 1H), 8.27 (d, J = 7.8 Hz, 1H), 7.92 (t, J = 7.7 Hz, 1H),
7.74 (br.s, 1H), 7.54 – 7.49 (m, 1H), 7.29 (d, J = 9.3 Hz, 1H),
1
3
7
.85 – 7.73 (m, 2H), 7.57 – 7.49 (m, 1H), 2.67 (s, 3H) (ppm).
C
13
NMR (100 MHz, CDCl ) δ = 162.5, 149.1, 144.6, 148.3, 142.1,
3.88 (s, 3H) (ppm). C NMR (100 MHz, CDCl ) δ = 163.3,
3
3
1
38.1, 136.3, 127.2, 126.8, 122.8 , 122.6 , 117.3, 21.5 (ppm). IR
155.2, 149.6, 148.7, 137.8,137.7, 128.4, 126.9, 123.7, 123.2,
(
(
in KBr): ν = 3550, 3472, 3415, 3232, 3135, 1616, 1401, 613
122.7, 109.1, 56.1 (ppm). MS (ESI): m/z(%) = 78 (60), 79 (45),
-
1
+
cm ). MS (ESI): m/z(%) = 78 (50), 79(43), 106 (47), 257.0 (100,
106 (55), 273.1 (80, M ). IR (in KBr): ν = 3550, 3471, 3413,
+
+
-1
M ). HRMS (ESI) (m/z) [C H N O +H ]: Calcd. 258.0873,
Found. 258.0874.
3234, 3142, 1619, 1401, 612 (cm ). HRMS (ESI) (m/z)
13
11
3
3
+
[C H N O +H ]: Calcd. 274.0822, Found. 274.0823.
13
11
3
4
4
.2.6 N-(2-Nitro-3,4-dimethylphenyl) 2-pyridinecarboxamide
4.2.10 N-(2-Nitro-4-fluorophenyl) 2-pyridinecarboxamide (2i)
(2e)
Follow the general procedure, 2i was obtained as yellow
solid with n-hexane/dichlormethane (10/1) used as eluent in 72%
yield (93.9 mg). Melting point: 179 – 180 C. H NMR (400 MHz,
Follow the general procedure, 2e was obtained as yellow
solid with n-hexane/dichlormethane (10/1) used as eluent in 68%
yield (92.1 mg). Melting point: 177 – 178 C. H NMR (400
o
1
o
1
CDCl ) δ = 12.67 (s, 1H), 9.14 – 9.02 (m, 1H), 8.73 (br, 1H),
3
MHz, CDCl ) δ = 12.71 (s, 1H), 8.82 (s, 1H), 8.73 (s, 1H), 8.27
8.28 (d, J = 7.4 Hz, 1H), 8.04 – 7.88 (m, 2H), 7.54 (br, 1H), 7.46
3
13
(
d, J = 7.2 Hz, 1H), 8.04 (s, 1H), 7.92 (t, J = 6.9 Hz, 1H), 7.52 (d,
(t, J = 7.6 Hz, 1H) (ppm). C NMR (100 MHz, CDCl ) δ = 163.5,
3
13
J = 3.3 Hz, 1H), 2.39 (s, 3H), 2.31 (s, 3H) (ppm). C NMR (100
157.2 (d, JC-F = 247.7 Hz), 149.2, 148.8, 137.8, 137.3 (d, JC-F =
MHz, CDCl ) δ = 163.5, 149.7, 148.8, 146.6, 137.7, 134.9, 132.7,
7.9 Hz), 131.3 (d, JC-F= 2.9 Hz), 127.2, 124.0 (d, JC-F= 7.3 Hz),
3
1
32.5, 126.9, 126.3, 122.8, 122.7, 20.7, 19.4 (ppm). IR (in KBr):
123.3 (d, J = 22.0 Hz), 122.9, 112.7 (d, JC-F = 27.2 Hz) (ppm).
C-F
19
ν = 3550, 3474, 3415, 3235, 2921, 2851, 2360, 2341, 1615, 668,
6
F NMR (375 MHz, CDCl ) δ = 115.92 (ppm). MS (ESI): m/z
3
-
1
+
20 (cm ). MS (ESI): m/z(%) = 78 (65), 79 (43), 106 (47), 271.0
(%) = 78 (75), 79 (40), 106 (47), 261.0 (100, M ). IR (in KBr): ν
= 3550, 3473, 3415, 3232, 3137, 1639, 1615, 1401, 619 (cm ).
HRMS (ESI) (m/z) [C H FN O +H ]: Calcd. 262.0622, Found.
+
+
-1
(100, M ). HRMS (ESI) (m/z) [C H N O +H ]: Calcd.
14
13
3
3
+
2
72.1030, Found. 272.1032.
12
8
3
3
2
62.0627.
4
.2.7 N-(2-Nitro-4-ethylphenyl) 2-pyridinecarboxamide (2f)
Follow the general procedure, 2f was obtained as yellow
4
.2.11 N-(2-Nitro-4-chlorophenyl) 2-pyridinecarboxamide
(2j)
solid with n-hexane/dichlormethane (10/1) used as eluent in 70%
o
1
yield (94.8 mg).Melting point: 114 – 115 C. H NMR (400 MHz,
Follow the general procedure, 2j was obtained as yellow
solid with n-hexane/dichlormethane (10/1) used as eluent in 79%
yield (109.4 mg). Melting point: 185 – 186 C. H NMR (400
CDCl ) δ = 12.64 (s, 1H), 8.91 (d, J = 8.6 Hz, 1H), 8.73 (d, J =
.4 Hz, 1H), 8.28 (d, J = 7.8 Hz, 1H), 8.08 (br.s, 1H), 7.92 (t, J =
.7 Hz, 1H), 7.53 (dd, J = 12.6, 7.8 Hz, 2H), 2.72 (q, J = 7.6 Hz,
H), 1.28 (t, J = 7.6 Hz, 3H) (ppm). C NMR (100 MHz, CDCl3)
δ = 163.5, 149.6, 148.8, 140.1, 137.7, 137.2, 135.6, 132.4, 127.0,
24.7, 122.8, 122.3, 28.1, 15.3 (ppm). MS (ESI): m/z(%) = 78
65), 79 (43), 106 (47), 271.0 (85, M ). IR (in KBr): ν = 3550,
472, 3415, 3232, 3136, 1615, 1401, 620 (cm ). HRMS (ESI)
m/z) [C H N O +H ]: Calcd. 272.1030, Found. 272.1037.
3
o
1
4
7
2
MHz, CDCl ) δ = 12.71 (s, 1H), 9.04 (d, J = 8.6 Hz, 1H), 8.73
3
13
(br.s, 1H), 8.27 (d, J = 7.5 Hz, 2H), 7.93 (t, J = 7.0 Hz, 1H), 7.65
13
(d, J = 8.8 Hz, 1H), 7.54 (br.s, 1H) (ppm). C NMR (100 MHz,
1
(
CDCl ) δ = 163.6, 149.1, 148.8, 137.9, 137.2, 135.8, 133.4, 128.6,
3
+
127.3, 125.7, 123.4, 122.9 (ppm). MS (ESI): m/z (%) = 78 (54),
-
1
+
3
(
79(45), 106 (53), 242 (30), 277.0 (100, M ). IR (KBr): ν = 3551,
+
-1
3473, 3415, 3231, 3136, 1615, 1401, 619 (cm ). HRMS (ESI)
14
13
3
3
+
(
m/z) [C H ClN O +H ]: Calcd. 278.0327, Found. 278.0331.
12
8
3
3
4
.2.8 N-(2-Nitro-4-tert-butylphenyl) 2-pyridinecarboxamide
(2g)
4.2.12 N-(2-Nitro-4-bromophenyl) 2-pyridinecarboxamide
2k)
(
Follow the general procedure, 2g was obtained as yellow
solid with n-hexane/dichlormethane (10/1) used as eluent in 81%
yield (121.1 mg). Melting point: 96 – 97 C. H NMR (400 MHz,
Follow the general procedure, 2k was obtained as yellow
solid with n-hexane/dichlormethane (10/1) used as eluent in 68%
o
1
o
1
CDCl ) δ = 12.62 (s, 1H), 8.91 (d, J = 8.7 Hz, 1H), 8.72 (br, 1H),
yield (108.8 mg). Melting point: 196 – 197 C. H NMR (400
3
6
8
1
.32 – 8.20 (m, 2H), 7.91 (t, J = 7.7 Hz, 1H), 7.73 (d, J = 8.8 Hz,
H), 7.52 (d, J = 4.1 Hz, 1H), 1.36 (s, 9H) (ppm). C NMR (100
MHz, d -acetone) δ = 8.96 (d, J = 9.0 Hz, 1H), 8.78 (d, J = 2.1
13
Hz, 1H), 8.42 (s, 1H), 8.26 (d, J = 7.6 Hz, 1H), 8.12 (t, J = 7.5
1
3
MHz, CDCl ) δ = 163.4, 149.6, 148.7, 147.2, 137.7, 137.0, 133.2,
Hz, 1H), 7.99 (d, J = 9.0 Hz, 1H), 7.77 – 7.69 (m, 1H). C NMR
3
1
32.1, 126.9, 122.8, 122.4, 122.0, 34.7, 31.1 (ppm). MS (ESI):
(100 MHz, CDCl ) δ = 163.6, 149.2, 148.8, 138.7, 137.9, 137.4,
3
+
m/z (%) = 78 (70), 79(55), 106 (50), 299.1 (90, M ). IR (in KBr):
ν = 3549, 3470, 3413,3151, 1639, 1618, 1401, 620 (cm ). HRMS
133.9, 128.6, 127.3, 123.6, 122.9, 115.5 (ppm). MS (ESI): m/z
-
1
+
(%) = 78 (65), 79(43), 106 (47), 242 (30), 320.0 (93, M ). IR (in
+
-1
(ESI) (m/z) [C H N O +H ]: Calcd. 300.1343, Found.
KBr): ν = 3550, 3473, 3413, 3232, 3126, 1615, 1401, 620 (cm ).
16
17
3
3
+
3
00.1349.
HRMS (ESI) (m/z) [C H BrN O +H ]: Calcd. 321.9822, Found.
12
8
3
3
3
21.9827.
4
.2.9 N-(2-Nitro-4-methoxyphenyl) 2-pyridinecarboxamide
(2h)
4.2.13 N-(2-Nitro-4-iodophenyl) 2-pyridinecarboxamide (2l)

6
Tetrahedron
MANUFo
Follow the general procedure, 2l was o
A
bta
C
in
C
ed
E
a
P
s
T
ye
E
llo
D
w
S
ll
C
ow
R
t
I
h
P
e
T
general procedure, 2q was obtained as yellow
solid with n-hexane/dichlormethane (10/1) used as eluent in 71%
yield (130.9 mg). Melting point: 190 – 191 C. H NMR (400
solid with n-hexane/dichlormethane (10/1) used as eluent in 58%
o
1
o
1
yield (78.6 mg). Melting point: 121 – 122 C. H NMR (400
MHz, CDCl ) δ = 12.72 (s, 1H), 8.84 (d, J = 8.2 Hz, 1H), 8.73
MHz, CDCl ) δ = 12.77 (s, 1H), 8.90 (d, J = 8.5 Hz, 1H), 8.06 (s,
3
3
(
br.s, 1H), 8.57 (s, 1H), 8.27 (d, J = 6.8 Hz, 1H), 7.96 (d, J = 7.8
2H), 7.78 (t, J = 7.5 Hz, 1H), 7.49 (d, J = 8.5 Hz, 1H), 7.36 (d, J
= 7.5 Hz, 1H), 2.68 (s, 3H), 2.40 (s, 3H) (ppm). C NMR (100
13
13
Hz, 2H), 7.54 (s, 1H) (ppm). C NMR (100 MHz, CDCl ) δ =
3
1
1
1
3
63.6, 149.5, 148.8, 144.4, 137.9, 137.4 , 134.4, 134.4, 127.3,
MHz, CDCl ) δ = 163.6, 157.9, 148.7, 137.9, 136.8,133.5, 132.4,
3
23.7, 122.9, 85.1 (ppm). MS (ESI): m/z (%) = 78 (61), 79(32),
126.7, 125.9, 121.9, 119.8, 24.4, 20.7 (ppm). MS (ESI): m/z (%)
+
+
06 (54), 242 (35), 369.0 (85, M ). IR (in KBr): ν = 3553, 3473,
= 92 (73), 93(45), 120 (47), 271.1 (100, M ). IR (in KBr): ν =
-
1
-1
411, 3232, 3136, 2360, 1618, 1400, 617 (cm ). HRMS (ESI)
3551, 3472, 3415, 3229, 3142, 1615, 1401, 616 (cm ). HRMS
+
+
(m/z) [C H IN O +H ]: Calcd. 369.9683, Found. 369.9680.
(ESI) (m/z) [C H N O +H ]: Calcd. 272.1030, Found.
12
8
3
3
14 13
3
3
2
72.1039.
4
.2.14 2-Nitro-4-[(2-pyridinylcarbonyl)amino] ethyl benzoic
ester (2m)
4.2.18 N-(2-Nitro-4-methylphenyl) 2-quinolinylcarboxamide
2s)
(
Follow the general procedure, 2m was obtained as yellow
solid with n-hexane/dichlormethane (10/1) used as eluent in 60%
yield (94.5 mg). Melting point: 150 – 151 C. H NMR (400
Follow the general procedure, 2s was obtained as yellow
solid with n-hexane/dichlormethane (10/1) used as eluent in 72%
yield (110.5 mg). Melting point: 170 – 171 C. H NMR (400
o
1
o
1
MHz, CDCl ) δ = 12.94 (s, 1H), 9.14 (d, J = 8.6 Hz, 1H), 8.91 (s,
3
1
H), 8.73 (s, 1H), 8.29 (dd, J = 14.6, 8.5 Hz, 2H), 7.93 (t, J = 7.4
MHz, CDCl ) δ = 12.98 (s, 1H), 8.95 (d, J = 8.4 Hz, 1H), 8.39 –
3
Hz, 1H), 7.54 (s, 1H), 4.50 – 4.31 (m, 2H), 1.42 (t, J = 6.4 Hz,
8.32 (m, 2H), 8.29 (d, J = 8.3 Hz, 1H), 8.09 (s, 1H), 7.90 (d, J =
7.9 Hz, 1H), 7.81 (t, J = 7.2 Hz, 1H), 7.66 (t, J = 6.8 Hz, 1H),
7.52 (d, J = 8.3 Hz, 1H), 2.42 (s, 3H) (ppm). C NMR (100
13
3
1
1
1
3
H) (ppm). C NMR (100 MHz, CDCl ) δ = 164.4, 163.7, 149.0,
48.8, 138.0, 138.9, 136.4, 136.4, 127.7, 127.4, 125.5, 123.0,
3
13
21.6 , 61.8, 14.4 (ppm). MS (ESI): m/z (%) = 78 (71), 79 (36),
MHz, CDCl ) δ = 163.6, 149.2, 146.6, 137.9, 136.9, 136.8, 133.7,
3
+
06 (55), 315.1 (83, M ). IR (in KBr): ν = 3550, 3472, 3416,
132.5, 130.6, 130.4 129.7, 128.7, 127.7, 125.9, 121.9, 118.8, 20.8
-
1
+
231, 3139, 1618, 1401, 616 (cm ). HRMS (ESI) (m/z)
(ppm). MS (ESI): m/z(%) = 128 (63), 156 (41), 307.1 (90, M ).
+
[
C H N O +H ]: Calcd. 316.0928, Found. 316.0929.
IR (in KBr): ν = 3550, 3472, 3415, 3148, 3136, 1615, 1401, 618
15
13
3
5
-
1
+
(
cm ). HRMS (ESI) (m/z) [C H N O +H ]: Calcd. 308.1030,
17 13 3 3
Found. 308.1031.
4
.2.16 N-(2-Nitro-4-trifluoromethylphenyl) 2-
pyridinecarboxamide (2n)
4
.2.19 N-(2-Nitro-4-methylphenyl) 2-thiophenylcarboxamide
(2t)
Follow the general procedure, 2n was obtained as yellow
solid with n-hexane/dichlormethane (10/1) used as eluent in 62%
yield (96.4 mg). Melting point: 174 – 175 C. H NMR (400
o
1
Follow the general procedure, 2t was obtained as yellow
solid with n-hexane/dichlormethane (10/1) used as eluent in 48%
yield (62.9 mg). Melting point: 144 – 145 C. H NMR (400
MHz, CDCl ) δ = 12.95 (s, 1H), 9.25 (d, J = 7.3 Hz, 1H), 8.75 (
3
o
1
br.s, 1H), 8.56 (s, 1H), 8.29 (d, J = 4.5 Hz, 1H), 7.93 (m, 2H),
1
3
7
1
.57 (br.s, 1H) ppm. C NMR (100 MHz, CDCl ) δ = 163.8,
MHz, CDCl ) δ = 11.16 (s, 1H), 8.75 (d, J = 8.3 Hz, 1H), 8.02
3
3
48.9, 137.96, 137.5, 136.3, 132.3 (q, JC-F= 3.1 Hz), 127.5, 123.7
(br.s, 1H), 7.69 (br.s, 1H), 7.60 (br.s, 1H), 7.47 (d, J = 8.5 Hz,
13
(
q, JC-F = 3.7 Hz), 123.1, 122.6, 125.5 (q, JC-F= 34.6 Hz), 123.0
1H), 7.15 (d, J = 3.2 Hz, 1H), 2.37 (s, 3H) (ppm). C NMR (100
19
(q, JC-F= 271.9 Hz) (ppm). F NMR (375 MHz, CDCl ) δ =
MHz, CDCl ) δ = 160.1, 139.3, 137.2, 135.9, 133.6, 132.8, 132.2,
3
3
6
3
2
2.57 (ppm). MS (ESI): m/z (%) = 78 (47), 79 (30), 106 (53),
129.1, 128.2, 125.7, 121.8, 20.6 (ppm). MS (ESI): m/z (%) = 83
+
+
11.0 (94, M ). IR (in KBr): ν = 3551, 3472, 3418, 3231, 3140,
(60), 84 (45), 111 (46), 262.1 (100, M ). IR (in KBr): ν = 3549,
-
1
-1
355, 2340, 1616, 1401, 620 (cm ). HRMS (ESI) (m/z)
3473, 3414, 3143, 1618, 1401, 620 (cm ). HRMS (ESI) (m/z)
+
+
[
C H F N O +H ]: Calcd. 312.0591, Found. 312.0585.
[C H N O S+H ]: Calcd.263.0485, Found 263.0491.
13
8
3
3
3
12 10
2
3
4
.2.16 N-(2-Nitro-4-methylphenyl) 3-methyl-2-
4.2.20 N-(4-Methyl-2-nitrophenyl) benzamide (2u)
pyridinecarboxamide (2p)
Follow the general procedure, 2u was obtained as yellow
solid with n-hexane/dichlormethane (10/1) used as eluent in 70%
yield (89.6 mg). Melting point: 142 – 143 C. H NMR (400
Follow the general procedure, 2p was obtained as yellow
solid with n-hexane/dichlormethane (10/1) used as eluent in 68%
yield (92.1 mg). Melting point: 192 – 193 C. H NMR (400
o
1
o
1
MHz, CDCl ) δ = 11.22 (s, 1H), 8.85 (d, J = 8.5 Hz, 1H), 8.04
3
MHz, CDCl ) δ = 12.74 (s, 1H), 8.86 (d, J = 8.4 Hz, 1H), 8.57 (s,
(br.s, 1H), 7.96 (d, J = 7.3 Hz, 2H), 7.57 (d, J = 6.5 Hz, 1H), 7.52
(d, J = 8.0 Hz, 3H), 2.39 (s, 3H) (ppm). C NMR (100 MHz,
3
13
1
1
H), 8.05 (s, 1H), 7.66 (d, J = 7.6 Hz, 1H), 7.49 (d, J = 8.5 Hz,
13
H), 7.43 – 7.38 (m, 1H), 2.80 (s, 3H), 2.41 (s, 3H) (ppm).
C
CDCl ) δ = 165.6, 137.2, 136.3, 134.1, 133.7, 132.9, 132.6,
3
NMR (100 MHz, CDCl ) δ = 164.9, 146.6, 146.1, 141.4, 137.1,
129.1, 127.4, 125.7, 122.1, 20.7 (ppm). MS (ESI): m/z (%) = 77
3
+
1
36.6, 136.5, 133.4, 132.6, 126.6, 125.9, 121.9, 20.9, 20.7 (ppm).
(60), 105(37), 256.1 (100, M ). IR (KBr): ν = 3551, 3471, 3415,
+
-1
MS (ESI): m/z (%) = 92 (63), 93(41), 120 (47), 271.1 (100, M ).
IR (KBr): ν = 3550, 3471, 3413, 3232, 3136, 3142, 1619, 1401,
6
2
3424, 3139, 1615, 1401, 616 (cm ). HRMS (ESI) (m/z)
+
[C H N O +H ]: Calcd. 257.0921, Found. 257.0926.
14
12
2
3
-
1
+
18 (cm ). HRMS (ESI) (m/z) [C H N O +H ]: Calcd.
14 13 3 3
72.1030, Found. 272.1035.
4
.2.21 N-(4-Methyl-2-nitrophenyl)-P,P-diphenylphosphinic
amide (2x)
4
.2.17 N-(2-Nitro-4-methylphenyl) 6-methyl-2-
pyridinecarboxamide (2q)
Follow the general procedure, 2x was obtained as yellow
solid with n-hexane/dichlormethane (10/1) used as eluent in 48%

7
o
1
C
yield (84.7 mg). Melting point: 109 – 110 C
A
.
H
CENM
P
R
TE(4
D
00 MA4.
N
2.2
U
5
S
N-
C
(4
R
-N
I
itro-1-naphthyl) 6-methyl-2-
P
T
MHz, CDCl ) δ = 9.05 (d, J = 12.0 Hz, 1H), 8.00 (s, 1H), 7.93 –
pyridinecarboxamide (2b')
3
7
.82 (m, 4H), 7.59 – 7.45 (m, 7H), 7.18 (d, J = 8.5 Hz, 1H), 2.28
13
(s, 3H) (ppm). C NMR (100 MHz, CDCl ) δ = 137.2, 136.8,
3
Follow the general procedure, 2b' was obtained as yellow
solid with n-hexane/dichlormethane (10/1) used as eluent in 71%
yield (108.9 mg). Melting point: 162 – 163 C. H NMR (400
1
1
35.6 (d, JC-P = 6.6 Hz), 132.8 (d, JC-P = 2.8 Hz), 131.7 (d, JC-P
=
o
1
0.3 Hz), 131.4(d, JC-P=129.3Hz ), 131.2, 129.2 (d, JC-P= 13.2
31
Hz), 126.0, 120.6 (d, JC-P= 5.1 Hz), 20.4 (ppm). P NMR (160
MHz, CDCl ) δ = 19.5 (ppm). MS (ESI): m/z(%) = 218.1 (55),
3
1
MHz, CDCl ) δ = 11.28 (s, 1H), 8.77 (d, J = 8.2 Hz, 1H), 8.68 (d,
3
3
J = 8.6 Hz, 1H), 8.38 (d, J = 8.6 Hz, 1H), 8.20 – 8.11 (m, 2H),
+
52.1 (100, M ). IR (in KBr): ν = 3550, 3472, 3415, 3232, 3130,
7
1
.86 (t, J = 7.6 Hz, 1H), 7.80 – 7.70 (m, 2H), 7.43 (d, J = 7.7 Hz,
-
1
13
638, 1618, 1401, 620 (cm ). HRMS (ESI) (m/z)
H), 2.74 (s, 3H) (ppm). C NMR (100 MHz, CDCl ) δ = 162.6,
3
+
[
C H N O P+H ]: Calcd.353.1050, Found 353.1054.
19 17 2 3
157.6, 148.6, 142.3, 138.7, 138.3, 129.5, 127.7, 127.1, 126.5,
26.0, 125.8, 124.5, 120.6, 120.0, 114.9, 24.6 (ppm). MS (ESI):
1
+
4
.2.22 N-(4-Methyl-2-nitrophenyl)-P,P-
m/z (%) = 92.1 (65), 120 (51), 307.2 (95, M ). IR (KBr): ν =
3550, 3472, 3416, 3230, 3135, 1640, 1615, 1401, 619 (cm ).
HRMS (ESI) (m/z) [C H N O +H ]: Calcd. 308.1030, Found.
-1
phenylmethylphosphonic amide (2y)
+
17
13
3
3
3
08.1029.
Follow the general procedure, 2y was obtained as yellow
solid with n-hexane/dichlormethane (10/1) used as eluent in 42%
yield (64.3 mg). Melting point: 72 – 73 C. H NMR (400 MHz,
o
1
4.2.26 N-(4-Nitro-1-naphthyl) 3-fluoro-2-
CDCl ) δ = 8.88 (d, J = 8.0 Hz, 1H), 8.00 (s, 1H), 7.88 (dd, J =
pyridinecarboxamide (2c')
3
1
7
3.5, 7.4 Hz, 2H), 7.59 (t, J = 7.1 Hz, 1H), 7.56 – 7.47 (m, 3H),
13
.28 (s, 1H), 3.87 (d, J = 11.5 Hz, 3H), 2.31 (s, 3H) (ppm).
C
Follow the general procedure, 2c' was obtained as yellow
solid with n-hexane/dichlormethane (10/1) used as eluent in 48%
yield (75.6 mg). Melting point: 132 – 133 C. H NMR (400
NMR (100 MHz, CDCl ) δ = 137.3, 136.0 (d, J = 4.1 Hz),
1
1
Hz ), 126.0, 119.63 (d, J = 3.4 Hz), 52.36 (d, JC-P = 5.6 Hz),
2
3
C-P
o
1
35.3 (d, JC-P= 8.2 Hz), 133.1 (d, JC-P = 3.0 Hz), 131.8 (d, JC-P
=
0.5 Hz), 131.1, 129.0 (d, JC-P = 14.9 Hz), 128.7 (d, JC-P = 174
MHz, CDCl ) δ = 11.02 (s, 1H), 8.71 (dd, J = 28.0, 8.4 Hz, 2H),
3
C-P
8.58 (br.s, 1H), 8.37 (d, J = 8.6 Hz, 1H), 8.14 (d, J = 8.1 Hz, 1H),
31
13
0.4 (ppm). P NMR (160 MHz, CDCl ) δ = 18.14 (ppm). MS
3
+
7.88 – 7.44 (m, 4H) (ppm). C NMR (100 MHz, CDCl ) δ =
3
(ESI): m/z(%) = 155.0 (47), 306.3 (100, M ). IR (in KBr): ν =
1
5
60.3(d, JC-F = 275.5 Hz), 160.1 (d, JC-F = 5.9 Hz), 144.2(d, JC-F
.6 Hz), 142.6, 138.2, 137.0 (d, JC-F = 4.0 Hz), 129.6, 129.4 (d,
=
-
1
3
545, 3475, 3414, 3232, 3132, 1619, 1400, 622 (cm ). HRMS
+
(ESI) (m/z) [C H N O P+H ]: Calcd. 307.0842, Found.
14 15 2 4
JC-F = 5.3 Hz), 127.7, 127.3 (d, JC-F= 19.5 Hz), 126.5, 125.9,
19
3
07.0847.
1
25.8, 124.6, 120.6, 115.1 (ppm). F NMR (375 MHz, CDCl ) δ
3
=
117.3 (ppm). MS (ESI): m/z (%) = 96.0 (55), 97 (45), 124 (58),
+
4
.2.23 N-(4-Nitro-1-naphthyl) 2-pyridinecarboxamide (2z)
Follow the general procedure, 2z was obtained as yellow
311.0 (80, M ). IR (in KBr): ν = 3550, 3472, 3413, 3230, 3138,
-1
1
639, 1615, 1401, 620 (cm ). HRMS (ESI) (m/z)
+
[
C H FN O +H ]: Calcd. 312.0779, Found. 312.0785.
16 10 3 3
solid with n-hexane/dichlormethane (10/1) used as eluent in 76%
o
1
yield (111.3 mg). Melting point: 171 – 172 C. H NMR (400
4.2.27 N-(4-Nitro-1-naphthyl) 2-quinolinylcarboxamide (2d')
MHz, CDCl ) δ =11.19 (s, 1H), 8.72 (dd, J = 27.7, 8.8 Hz, 3H),
3
8
.37 (t, J = 8.5 Hz, 2H), 8.20 (d, J = 7.7 Hz, 1H), 7.99 (t, J = 7.0
Follow the general procedure, 2d' was obtained as yellow
solid with n-hexane/dichlormethane (10/1) used as eluent in 80%
yield (137.2 mg). Melting point: 203 – 204 C. H NMR (400
13
Hz, 1H), 7.76 (t, J = 8.1 Hz, 2H), 7.59 (br, 1H) (ppm). C NMR
100 MHz, CDCl ) δ = 162.4, 149.4, 148.4, 142.4, 138.5, 138.2,
o
1
(
1
1
3
29.6, 127.7, 127.3, 126.5, 125.9, 125.8, 124.5, 122.9, 120.7,
MHz, CDCl ) δ = 11.41 (s, 1H), 8.78 (d, J = 5.9 Hz, 1H), 8.72 (d,
3
14.9 (ppm). MS (ESI): m/z (%) = 78.0 (85), 79.0 (43), 106.0
J = 8.4 Hz, 1H), 8.43 (br.s, 2H), 8.40 (d, J = 8.7 Hz, 1H), 8.29 (d,
J = 7.0 Hz, 2H), 7.96 (d, J = 7.9 Hz, 1H), 7.88 (t, J = 7.3 Hz,
+
(52), 293.0 (100, M ). IR (in KBr): ν =3551, 3471, 3232, 3415,
-
1
1
3
3
135, 1615, 1401, 619 (cm ). HRMS (EI) (m/z)
1
H), 7.79 (d, J = 4.0 Hz, 2H), 7.72 (t, J = 6.9 Hz, 1H) (ppm).
C
+
[
C H N O +H ]: Calcd. 294.0873, Found. 294.0873.
16 11 3 3
NMR (100 MHz, CDCl ) δ = 162.6, 149.1, 146.4, 142.4, 138.6,
3
1
38.5, 130.9, 129.9, 129.9, 129.6, 128.8, 128.1, 127.8, 126.5,
4
.2.24 N-(4-Nitro-1-naphthyl) 3-methyl-2-
126.0, 125.0, 124.6, 120.7, 118.9, 115.0 (ppm). IR (KBr): ν =
-
pyridinecarboxamide (2a')
3551, 3473, 3413, 3228, 3138, 2357, 1639, 1615, 1401, 619 (cm
1
+
)
. MS (ESI): m/z(%) = 128.1 (55), 156 (63), 343.0 (80, M ).
+
HRMS (ESI) (m/z)[C H N O +H ]: Calcd. 344.1030, Found.
Follow the general procedure, 2a' was obtained as yellow
solid with n-hexane/dichlormethane (10/1) used as eluent in 62%
yield (95.2 mg). Melting point: 149 – 150 C. H NMR (400
20 13
3
3
3
44.1037.
o
1
MHz, CDCl ) δ = 11.53 (s, 1H), 8.77 (d, J = 8.5 Hz, 1H), 8.66 (d,
4.2.28 N-(4-Nitro-1-naphthyl) 2-thiophenylcarboxamide (2e')
3
J = 8.6 Hz, 1H), 8.58 (d, J = 3.9 Hz, 1H), 8.38 (d, J = 8.6 Hz,
1
7
H), 8.19 (d, J = 8.3 Hz, 1H), 7.75 (dd, J = 21.6, 7.5 Hz, 3H),
.49 – 7.45 (m, 1H), 2.86 (s, 3H) (ppm). C NMR (100 MHz,
Follow the general procedure, 2e' was obtained as yellow
solid with n-hexane/dichlormethane (10/1) used as eluent in 52%
yield (77.5 mg). Melting point: 175 – 176 C. H NMR (400
13
o
1
CDCl ) δ = 163.8, 146.2, 145.8,142.1, 141.8, 139.1, 137.0, 129.5,
1
3
27.5, 126.9, 126.5, 126.1, 125.9, 124.5, 120.9, 114.5, 20.9
MHz, CDCl ) δ = 8.70 (d, J = 8.7 Hz, 1H), 8.38 (br.s, 1H), 8.30
3
(ppm). MS (ESI): m/z (%) = 92.1 (74), 93.1 (47) 120 (46), 307.0
(
1
s, 2H), 7.97 (d, J = 8.4 Hz, 1H), 7.81 (s, 1H), 7.75 (t, J = 7.6 Hz,
+
1
3
(91, M ). IR (in KBr): ν = 3550, 3472, 3415, 3233, 3135, 1615,
H), 7.67 (dd, J = 10.0, 6.3 Hz, 2H), 7.22 (m, 1H) (ppm).
C
-
1
+
1
3
402, 619 (cm ). HRMS (ESI) (m/z) [C H N O ]+H : Calcd.
17 13 3 3
NMR (100 MHz, CDCl ) δ = 160.3, 143.2, 138.4, 137.9, 132.0,
3
08.1030, Found. 308.1029.
1
29.61,129.57, 128.4, 127.8,126.5, 125.3, 124.5, 120.58, 117.57
+
(ppm). MS (ESI): m/z(%) = 83.0 (60), 111 (55), 298.0 (85, M ).
IR (in KBr): ν = 3551, 3472, 3413, 3232, 3136, 1638, 1618,

8
Tetrahedron
+
-
1
1
401, 619 (cm ). HRMS (ESI) (m/z) [CAC
H
C
N
E
O
PTS+
E
H
D
]: MA4.
NU
2.3
3
S
4-
C
Br
R
omIPo-
T
2-nitroaniline (3b)
15
10
2
3
Calcd. 299.0485, Found. 299.0499.
.2.29 N-(4-Nitro-1-naphthyl) benzamide (2f')
After treatment with NaOH, 3b was obtained as red solid with n-
hexane/ethyl acetate (10/1) used as eluent in 92% yield (99.4
mg). Melting point: 86 – 87 C. H NMR (400 MHz, CDCl ) δ =
4
o
1
3
8
6
1
1
3
.23 (s, 1H), 7.41 (d, J = 8.8 Hz, 1H), 6.73 (d, J = 8.8 Hz, 1H),
Follow the general procedure, 2f' was obtained as yellow solid
with n-hexane/dichlormethane (10/1) used as eluent in 65% yield
13
.15 (s, 2H) (ppm). C NMR (100 MHz, CDCl ) δ = 143.7,
3
o
1
38.6, 132.5, 128.4, 120.5, 107.9 (ppm). MS (ESI): m/z(%) =
(94.9 mg). Melting point: 202 – 203 C. H NMR (400 MHz,
+
22.0 (45), 216.0 (100, M ). IR (in KBr): ν= 3550, 3473, 3414,
CDCl ) δ = 8.74 (d, J = 8.6 Hz, 1H), 8.53 (br, 1H), 8.42 (d, J =
3
-
1
228, 3132, 1639, 1615, 1401, 620 (cm ). HRMS (ESI) (m/z)
8
7
2
1
1
.5 Hz, 1H), 8.35 (d, J = 8.5 Hz, 1H), 8.01 (d, J = 7.8 Hz, 3H),
.78 (t, J = 7.6 Hz, 1H), 7.72 – 7.63 (m, 2H), 7.59 (t, J = 7.3 Hz,
+
[
C H BrN O +H ]: Calcd. 216.9607, Found. 216.9609.
6 5 2 2
13
H) (ppm). C NMR (100 MHz, CDCl ) δ = 166.1, 143.2, 138.4,
3
34.3,132.8, 129.6, 129.3, 127.8, 127.4, 125.4, 124.6, 120.5,
4.2.34 4-Nitronaphthalen-1-amine (3c)
17.4 (ppm). MS (ESI): m/z (%) =77.0 (42), 105 (53), 292.1
+
(100, M ). IR (in KBr): ν = 3551, 3471, 3415, 3139, 2360, 1615,
After treatment with NaOH, 3c was obtained as yellow solid with
n-hexane/ethyl acetate (10/1) used as eluent in 93% yield (87.4
mg). Melting point: 172 – 173 C. H NMR (400 MHz, CD OD)
-
1
+
1
2
401, 619 (cm ). HRMS (ESI) (m/z) [C H N O +H ]: Calcd.
17 12 2 3
o
1
93.0921, Found. 293.0935.
3
δ = 8.92 (d, J = 8.7 Hz, 1H), 8.35 (d, J = 8.8 Hz, 1H), 8.10 (d, J =
8.4 Hz, 1H), 7.65 (t, J = 7.6 Hz, 1H), 7.46 (t, J = 7.5 Hz, 1H),
4
.2.30 N-(4-Nitro-2-methyl-1-naphthyl)
2-
13
pyridinecarboxamide (2g')
6.63 (d, J = 8.8 Hz, 1H) (ppm). C NMR (100 MHz, CD OD) δ
3
=
154.7, 134.4, 131.1, 129.6, 126.2, 125.2, 123.7, 122.6, 106.4
+
(ppm). MS (EI): m/z(%) = 142.0 (30), 188.1 (100, M ). IR (in
Follow the general procedure, 2g' was obtained as yellow solid
with n-hexane/dichlormethane (10/1) used as eluent in 42% yield
-1
KBr): ν = 3550, 3472, 3415, 3133, 1618, 1401, 620 (cm ).
HRMS (ESI) (m/z) [C H N O +H ]: Calcd. 189.0659, Found.
+
o
1
(
64.5 mg). Melting point: 158 – 159 C. H NMR (400 MHz,
10
8
2
2
1
89.0664.
CDCl ) δ = 10.09 (s, 1H), 8.72 (s, 1H), 8.57 (d, J = 8.3 Hz, 1H),
3
8
7
2
1
1
.33 (d, J = 7.4 Hz, 1H), 8.21 (s, 1H), 8.07 (d, J = 8.2 Hz, 1H),
.98 (t, J = 7.0 Hz, 1H), 7.67 (d, J = 8.0 Hz, 1H), 7.65 – 7.56 (m,
Acknowledgments
13
H), 2.54 (s, 3H) (ppm). C NMR (100 MHz, CDCl ) δ = 162.9,
3
49.2, 148.5, 145.3, 138.0, 136.1, 132.3, 131.4, 128.8, 128.0,
This work was financially supported by the Science and
Technology Planning Project of Guangzhou City
27.2, 127.1, 124.62, 123.59, 123.4, 122.9, 19.1 (ppm). MS (ESI):
+
m/z (%) =78.0 (85), 79.0 (50), 106 (53), 307.1 (95, M ). IR (in
KBr): ν = 3550, 3478, 3412, 3229, 3136, 1639, 1619, 1401, 621
(201607010349), the Science and Technology Planning Project
of Shenzhen City (20180205162723338), the Science and
Technology Planning Project of Guangdong Province
(2015A010105013) and the National Natural Science Foundation
of China (21102187), Pearl River Technology New Star
-
1
+
(cm ). HRMS (ESI) (m/z) [C H N O +H ]: Calcd.308.1030,
17 13 3 3
Found. 308.1029.
(201710010183).
4
.2.31 N-(1-Nitro-2-naphthyl) 2-pyridinecarboxamide (2h')
Supplementary Material
Supporting Information is available via Http://
References
Follow the general procedure, 2h' was obtained as yellow solid
with n-hexane/dichlormethane (10/1) used as eluent in 58% yield
o
1
(84.9 mg). Melting point: 176 – 177 C. H NMR (400 MHz,
CDCl ) δ = 11.55 (s, 1H), 8.74 (d, J = 10.0 Hz, 2H), 8.30 (d, J =
3
7
2
.7 Hz, 1H), 8.06 (d, J = 8.9 Hz, 2H), 7.92 (dd, J = 20.4, 8.0 Hz,
H), 7.66 (t, J = 7.5 Hz, 1H), 7.55 (s, 2H) (ppm). C NMR (100
13
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3
1
30.6, 129.4, 128.4, 127.2, 126.5, 125.8, 122.8, 122.3, 120.5
(
ppm). MS (ESI): m/z (%) = 78.0 (80), 79.0 (55), 106 (60), 293.1
+
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δ = 7.52 (s, 1H), 7.06 (d, J = 9.0 Hz, 1H), 6.76 (d, J = 8.9 Hz,
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6
1
H), 5.93 (s, 2H), 3.78 (s, 3H) (ppm). C NMR (100 MHz,
[
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(
1
ppm). IR (in KBr): ν = 3551, 3473, 3415, 3232, 3134, 1637,
-
1
3,
615, 1401, 619 (cm ). MS (ESI): m/z (%) = 122.0 (40), 168.0
2
[
+
+
(100, M ). HRMS (ESI) (m/z) [C H N O +H ]: Calcd. 169.0608,
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[
[
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