Silver-Catalyzed Chemo- and Regioselective Nitration of Anilides

Article abstract of DOI:10.1002/ejoc.201800779

A new and efficient Ag-catalyzed method for the nitration of anilides by using sodium nitrite as a cheap and available NO₂ source has been developed. This C–H functionalization reaction is ortho-selective, achieves moderate to high yields and shows excellent functional group tolerance. Furthermore, it provides a novel approach to ortho-nitrated anilides, which are very tricky to access with traditional methods.

Full text of DOI:10.1002/ejoc.201800779

DOI: 10.1002/ejoc.201800779
Full Paper
C–H Functionalization
Silver-Catalyzed Chemo- and Regioselective Nitration of
Anilides
Ebrahim Kianmehr*[a] and Sepideh Bahrami Nasab[a]
Abstract: A new and efficient Ag-catalyzed method for the yields and shows excellent functional group tolerance. Further-
nitration of anilides by using sodium nitrite as a cheap and
available NO2 source has been developed. This C–H functionali-
zation reaction is ortho-selective, achieves moderate to high
more, it provides a novel approach to ortho-nitrated anilides,
which are very tricky to access with traditional methods.
Introduction
ortho C–H bond nitration of benzoic acid derivatives using so-
dium nitrite as a nitrating source was demonstrated by Tan in
2014.[10] Gooßen and co-workers reported copper-mediated or-
tho-nitration of (hetero)arenecarboxylic acids in the presence of
AgNO2 in 2014.[11] A combination of AgNO2 with TEMPO was
used for highly selective nitration of olefins by Maiti in 2013.[12]
Unfortunately, all of these metal-mediated methods involve use
of large amounts of metals. Recently, transition metal-catalyzed
coupling methods for nitration of aromatic compounds have
been further investigated. Copper catalyzed ipso-nitration of
haloarenes with KNO2 was reported by Kantam in 2012.[13] Saito
et al. developed nitration of aromatic halides in the presence
of catalytic amounts of Cu bronze with nBu4NNO2 in 2005.[14]
Buchwald and co-workers developed a general Pd catalyzed
nitration of prefunctionalized aryl chlorides, triflates, and nona-
flates with NaNO2 as a simple nitro source.[15] CuII-catalyzed
nitration of aryl boronic acids in the presence of NaNO2 was
reported by Fu in 2011.[16] Li and co-workers reported a signifi-
cant Rh-catalyzed C–H nitration of arenes with NaNO2 in the
presence of a costly hypervalent iodine oxidant in 2013.[17] Cop-
per-catalyzed nitration of quinolines at the C5 or C7 position
using NaNO2 was reported by Zhang in 2016.[18] Recently Sun
reported the ortho-C–H nitration of ureas in the presence of
CuCl2·2H2O as catalyst and Fe(NO3)3·9H2O as a nitro source.[19]
A palladium-catalyzed chelation-assisted ortho-nitration of aryl
ketone with AgNO2 was demonstrated by Liu's group in
2013.[20] Xu et al. reported nitration of quinoxaline in the pres-
ence of catalytic amounts of Pd(OAc)2 and AgNO2 as a nitrating
source in 2010.[21] Silver-catalyzed decarboxylative nitroaminox-
ylation of phenylpropiolic acids using tert-butyl nitrite (TBN)
was described by Mao in 2012.[22] Regioselective nitration of
anilines and anilides have been of great interest in recent years.
A palladium-catalyzed, heteroatom-directed method for C–H
nitration of anilines with AgNO2 has been described by Kapur
in 2016 [Scheme 1, Equation (1)].[23] Copper(II)-catalyzed ortho-
nitration of aniline derivatives protected as 1-aryl-5-aminotet-
razolyl using Fe(NO3)3·9H2O was described by Punniyamurthy
in 2015 [Scheme 1, Equation (2)].[24] An efficient Fe(NO3)3·9H2O
promoted ortho-nitration of aniline derivatives has been devel-
oped by Huo in 2018 [Scheme 1, Equation (3)].[25] Copper-cata-
Nitroarene compounds or intermediates are important organo-
precursors for the synthesis of pharmaceuticals, dyes, explosives
and other valuable chemical substances. Therefore, finding a
highly efficient method for the nitration of aromatic derivatives
is a topic of great interest for organic chemists.[1] For example,
flutamide has been used in treatment of metastatic carcinoma
of the prostate[2] and niclosamide have been shown to have
powerful cestodicidal activity.[3] 2-Nitro-N-acylanilines are criti-
cal intermediates in the synthesis of phenanthro[2,3-d]imidaz-
ole derivatives which show useful antibacterial or antifungal
properties (Figure 1, compound A).[4]
Figure 1. Some biologically active nitroarene compounds.
Traditional methods of preparing nitroarenes use mixed
strong-acid systems such as (HNO3/H2SO4)[5] or N2O5[6] and suf-
fer from harsh reaction conditions, low regioselectivity, and lim-
ited functional group tolerance. In this regard, using metal
nitrate salts such as Bi(NO3)3·5H2O, Ca(NO3)2, Ni(NO3)2·6H2O
and other nitronium salts in stoichiometric amounts has be-
come commonplace.[7–9] However, hazardous acidic conditions
have been overcome by the use of nitrate salt reagents. Unfor-
tunately, mostly these reagents are expensive, difficult to pre-
pare and produce high quantities of metal oxides as unfavora-
ble by products. In recent years chelation-assisted aromatic C–H
ortho-nitration has attracted some interest. A copper-mediated
[a] School of Chemistry, College of Science, University of Tehran,
Tehran, Iran
E-mail: kianmehr@khayam.ut.ac.ir
Supporting information and ORCID(s) from the author(s) for this article are
available on the WWW under https://doi.org/10.1002/ejoc.201800779.
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lyzed nitration of protected anilines with HNO3 was reported ortho-nitro anilines from the corresponding anilides and sulfon-
by Carretero in 2014 [Scheme 1, Equation (4)].[26] Yan et al. used amides can be successfully achieved.[32]
a combination of tert-butyl nitrite (TBN) and a catalytic amount
of Cu(NO3)2·3H2O for the efficient aryl nitration of aromatic
amides [Scheme 1, Equation (5)].[27] Iron-mediated direct ortho-
nitration of anilides and aromatic sulfonamides was developed
by Chandrasekharam in 2016 [Scheme 1, Equation (6)].[28] Metal
free nitration of aromatic sulfonamides with tert-butyl nitrite
(TBN)[29] and NaNO2/PIFA[30] has been reported by Arns and
Nachtsheim separately. Conversely, less expensive silver com-
plexes were as of yet underutilized for C–H activation reaction,
with notable exceptions being accomplished only very re-
cently.[31] Herein we report a silver catalyzed regioselective
ortho-nitration of anilides and also aromatic sulfonamides by
which a general and regiospecific synthesis of substituted
Results and Discussion
To start our investigation, we chose N-phenylacetamide (1a) as
the substrate and sodium nitrite (1.0 equiv.) as the nitrating
agent. In order to optimize the reaction conditions, a series of
experiments with different parameters such as catalyst, solvent
and oxidant were performed for the typical reaction (Table 1).
Various conditions were screened to optimize the reaction con-
ditions (Table 1). A screening of catalysts revealed that AgNO2
gave the best result (Table 1, entry 1). The reaction was moni-
tored with different amounts of catalyst loading and the results
showed that 10 mol-% of AgNO2 was the best choice for com-
pletion of the reaction (Table 1, entries 1, 2). AgNO3 gave mod-
erate yield of the product and AgOAc, Ag2CO3 and palladium-
based catalysts such as Pd(OAc)2 and PdCl2 were found to be
inferior (Table 1, entries 3–7). Commonly used organic solvents
were screened and CH3CN gave the best result. Changing the
solvent to DMF and DMSO gave no product (Table 1, entries
8,9). When the reaction was conducted in DME, DCE, toluene
and PhCl moderate to low yields of the product was obtained
(Table 1, entries 10–13). The effect of a range of the oxidants
Table 1. Optimization of the reactions conditions.[a]
Catalyst [mol-
%]
Entry
Oxidant
Solvent Temp. [°C] Yield [%]
1
2
3
4
5
6
7
8
AgNO2(10)
AgNO2(5)
AgNO3(10)
AgOAc(10)
Ag2CO3(10)
Pd (OAc)2(10)
PdCl2(10)
AgNO2(10)
AgNO2(10)
AgNO2(10)
AgNO2(10)
AgNO2(10)
AgNO2(10)
AgNO2(10)
AgNO2(10)
AgNO2(10)
AgNO2(10)
AgNO2(10)
AgNO2(10)
AgNO2(10)
AgNO2(10)
AgNO2(10)
–
K2S2O8
K2S2O8
K2S2O8
K2S2O8
K2S2O8
K2S2O8
K2S2O8
K2S2O8
K2S2O8
K2S2O8
K2S2O8
K2S2O8
K2S2O8
(NH4)2S2O8
Na2S2O8
TBHP
CH3CN 110
CH3CN 110
CH3CN 110
CH3CN 110
CH3CN 110
CH3CN 110
CH3CN 110
79
42
37
trace
trace
0
0
0
0
49
51
36
27
52
61
0
0
0
0
DMF
DMSO
DME
DCE
110
110
110
110
9
10
11
12
13
14
15
16
17
18
19
20
21[b]
22[c]
23
24
toluene 110
PhCl 110
CH3CN 110
CH3CN 110
CH3CN 110
CH3CN 110
DTBP
Cu(OAc)2·H2O CH3CN 110
CuO
CH3CN 110
CH3CN 90
CH3CN 110
CH3CN 110
CH3CN 110
CH3CN 110
K2S2O8
K2S2O8
K2S2O8
K2S2O8
–
31
47
59(17)[d]
0
AgNO2(10)
0
[a] 1a (0.5 mmol), NaNO2 (1.0 equiv.), catalyst, oxidant (2.0 equiv.), solvent
(1.5 mL) were stirred at 110 °C for 16 h. [b] 50 mol-% of NaNO2 was used.
[c] 1.0 equiv. tert-butyl nitrite was used. [d] para product in parentheses.
Scheme 1. Literature precedence for nitration of aromatic anilide compounds.
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was examined and the results showed that K2S2O8 was more in Table 2. It was found that a variety of anilides with electron-
effective than others such as (NH4)2S2O8, Na2S2O8, TBHP, DTBP, donating and electron-withdrawing groups substituted on the
Cu(OAc)2·H2O and CuO (Table 1, entries 14–19). The reaction aromatic ring, were tolerated and good yields were obtained in
temperature was also varied and the best results were obtained all cases. Generally, the presence of electron-donating groups
at 110 °C. Upon decreasing the reaction temperature from 110 led to higher yields of the products (Table 2, 2b, 2c, 2d, 2g, 2h,
to 90 °C, the yield of the reaction decreased dramatically 2m, 2n, 2p, 2r, and 2t). Also, anilides bearing electron-with-
(Table 1, entry 20). By reducing the amount of NaNO2, as the drawing substituents such as halogens and nitro groups re-
nitrating agent, to 0.5 equiv. the yield of the reaction decreased sulted in products in moderate yields (Table 2, 2e, 2i, 2j, 2k, 2o
to 47 % (Table 1, entry 21). By using tert-butyl nitrite (TBN) as and 2q). Surprisingly, 4-methyl-N-(p-tolyl)benzenesulfonamide
the nitrating agent a mixture of ortho/para products was ob- also gave the desired product 2s in good yield (Table 2).
On the basis of previous reports,[33] a possible catalytic
mechanism for this transformation is illustrated in Scheme 2. At
first, arylsilver complex C is formed via coordination of silver
catalyst to the acetylamino directing group,[33b] which subse-
quently provides N-phenyl acetamide radical D and Ag0 which
is reoxidiszed to AgI in presence of K2S2O8. Intermediate D re-
acts with in situ generated NO2 radical[23,26,34] to give the ortho-
nitrated product 2b. To prove the radical mechanism, a control
reaction was carried out using 2,6-di-tert-butyl-4-methylphenol
(BHT) as a radical scavenger. As expected, when the reaction of
1b was carried out in the presence of BHT, no desired product
2b was observed.
tained (Table 1, entry 22). Notably, no reaction occurred in the
absence of a catalyst or an oxidant (Table 1, entries 23 and 24).
Once the optimized conditions for the desired nitration reac-
tion were established, the scope of the reaction with regard to
different anilides was investigated. The results are summarized
Table 2. Silver-catalyzed regioselective ortho-nitration of anilides.[a]
Scheme 2. Possible mechanism.
Conclusions
In conclusion, we have developed an efficient silver-catalyzed
method for regioselective ortho C–H bond nitration of anilides
using sodium nitrite in the presence of K2S2O8 as the oxidant
in acetonitrile via the highly valuable strategy of C–H bond acti-
vation. The reaction can be applied to numerous substrates
with good tolerance of both electron-deficient and electron-
rich functional groups, providing a simple and straightforward
way to synthesize of various ortho-nitro anilides using com-
monly available starting materials. Products of this reaction are
interesting targets to probe in pharmaceutical and petroleum
industries.[35]
Experimental Section
General Information: Solvents, K2S2O8, AgNO2, NaNO2 and aniline
derivatives were purchased from Merck. Other reagents were pur-
[a]
1 (0.5 mmol), Ag catalyst (10 mol-%), NaNO2 (1.0 equiv.), K2S2O8
(2.0 equiv.), in acetonitrile (1.5 mL) at 110 °C for 16 h.
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chased from commercial distributors and were used without further
1 H), 7.68 (br., 2 H), 7.11 (dd, J = 8.6, 2.1 Hz, 1 H), 6.97 (d, J = 8.6 Hz,
purification. Anilide[36] and aromatic sulfonamide[37] were synthe- 1 H), 2.25 (s, 3 H) ppm. 13C NMR (101 MHz, [D]Chloroform): δ =
sized according to the literature. Analytical thinlayer chromatogra- 175.0, 144.0, 139.1, 135.3, 132.2, 122.5,120.8, 29.7 ppm. MS (EI): m/z
phy (TLC) was performed on precoated silica gel60 F254 plates. The
products were purified by preparative column chromatography on
silica gel (0.063–0.200 mm, Merck). 1H NMR and 13C NMR spectra
were recorded with a Bruker DRX 400 and 500 Advance instrument
in CDCl3. Mass spectrometry was performed with an Agilent 5975C
VL MSD (ion source: EI+, 70 eV, 230 °C).
(%) = 196 (21) [M+], 194 (43), 180 (11), 153 (31), 138 (49), 107 (21),
79 (31), 43 (100). C8H8N2O4 (196.16): calcd. C 48.98, H 4.11, N 14.28;
found C 48.76, H 4.14, N 14.35.
N-(4-iodo-2-nitrophenyl)acetamide (2e):[25] The general proce-
dure was followed by using 4-Iodoacetanilide (0.5 mmol, 130 mg),
NaNO2 (69 mg, 0.5 mmol), K2S2O8 (270 mg, 1.0 mmol), and AgNO2
(8 mg, 10 mol-%). Purification by column chromatography (silica
gel; n-hexane/EtOAc, 2:1) gave product 2e (96 mg, 63 %) as a yellow
solid, m.p. 101–103 °C. 1H NMR (500 MHz): δ = 10.27 (br., 1 H), 8.54
General Procedure for the Synthesis of 2-nitroanilides: 10 mL
microwave vial was charged with an acetanilide derivative
(1.0 equiv., 0.5 mmol), NaNO2 (1.0 equiv.), AgNO2 (10 mol-%), K2S2O8
(2.0 equiv.) and CH3CN (1.5 mL). The vial was then sealed and im- (s, 1 H), 7.92 (d, J = 8.9 Hz, 1 H), 7.58 (d, J = 8.8 Hz, 1 H), 2.31 (s, 3
mersed in an oil bath at 110 °C, for 16 h. After this time, the mixture
was cooled to room temperature and then diluted with CH2Cl2 and
filtered. The residue was purified by column chromatography (n-
hexane/EtOAc, 2:1) to yield the desired product.
H) ppm. 13C NMR (101 MHz, [D]Chloroform): δ = 169.1, 144.5, 134.0,
123.7, 120.6, 84.8, 29.7 ppm. MS (EI): m/z (%) = 306 (14) [M+], 285
(44), 278 (18), 264 (100), 256 (34), 220 (31), 91 (27). C8H7IN2O3
(306.06): calcd. C 31.39, H 2.31, N 9.15; found C 31.50, H 2.33, N
9.10.
N-(2-nitrophenyl)acetamide (2a):[38] The general procedure was
followed by using acetanilide (0.5 mmol, 67 mg), NaNO2 (69 mg,
0.5 mmol), K2S2O8 (270 mg, 1.0 mmol), and AgNO2 (8 mg, 10 mol-
%). Purification by column chromatography (silica gel; n-hexane/
N-(2-nitrophenyl)pivalamide (2f):[27] The general procedure was
followed by using pivalamide (0.5 mmol, 88 mg), NaNO2 (69 mg,
0.5 mmol), K2S2O8 (270 mg, 1.0 mmol), and AgNO2 (8 mg, 10 mol-
EtOAc, 2:1) gave product 2a (71 mg, 79 %) as a yellow solid, m.p. %). Purification by column chromatography (silica gel; n-hexane/
90–91 °C. 1H NMR (500 MHz, [D]Chloroform): δ = 10.32 (br., 1 H), EtOAc, 2:1) gave product 2f (86 mg, 78 %) as a yellow solid, m.p.
1
8.77 (dd, J = 8.6, 1.4 Hz, 1 H), 8.21 (dd, J = 8.4, 1.6 Hz, 1 H), 7.65
99–100 °C. H NMR (400 MHz): δ = 10.79 (br., 1 H), 8.92–8.80 (m, 1
(ddd, J = 8.7, 7.2, 1.6 Hz, 1 H), 7.18 (ddd, J = 8.5, 7.3, 1.4 Hz, 1 H),
H), 8.27 (dd, J = 8.4, 1.6 Hz, 1 H), 7.68 (ddd, J = 8.7, 7.2, 1.6 Hz, 1
2.30 (s, 3 H) ppm. 13C NMR (101 MHz, [D]Chloroform): δ = 169.1, H), 7.20 (ddd, J = 8.6, 7.3, 1.4 Hz, 1 H), 1.28 (s, 9 H) ppm. 13C NMR
136.0, 125.8, 124.5, 124.0, 123.3, 122.2, 22.7 ppm. MS (EI): m/z (%) =
180 (11) [M+], 167 (75), 155 (83), 113 (25), 97 (37), 85 (77), 57 (100),
43 (25). C8H8N2O3 (180.16): calcd. C 53.33, H 4.48, N 15.55; found C
53.41, H 4.45, N 5.62.
(101 MHz, [D]Chloroform): δ = 174.0, 139.8, 136.1, 135.5, 125.8,
123.0, 122.1, 40.6, 27.5 ppm. MS (EI): m/z (%) = 222 (11), 118 (62),
109 (11), 98 (61), 84 (37), 69 (44), 58 (100). C11H14N2O3 (222.24):
calcd. C 59.45, H 6.35, N 12.61; found C 59.34, H 6.38, N 12.67.
N-(4-methyl-2-nitrophenyl)acetamide (2b):[39] The general proce-
N-(4-ethyl-2-nitrophenyl)pivalamide (2g): The general procedure
dure was followed by using 4-methylacetanilide (0.5 mmol, 74 mg),
was followed by using 4-ethylpivalamide (0.5 mmol, 102 mg),
NaNO2 (69 mg, 0.5 mmol), K2S2O8 (270 mg, 1.0 mmol), and AgNO2 NaNO2 (69 mg, 0.5 mmol), K2S2O8 (270 mg, 1.0 mmol), and AgNO2
(8 mg, 10 mol-%). Purification by column chromatography (silica (8 mg, 10 mol-%). Purification by column chromatography (silica
gel; n-hexane/EtOAc, 2:1) gave product 2b (84 mg, 87 %) as a yellow
solid, m.p. 87–89 °C. 1H NMR (500 MHz): δ = 10.22 (br., 1 H), 8.64
(d, J = 8.6 Hz, 1 H), 8.02 (d, J = 2.1 Hz, 1 H), 7.47 (dd, J = 8.7, 2.0 Hz,
1 H), 2.41 (s, 3 H), 2.29 (s, 3 H) ppm. 13C NMR (101 MHz, [D]Chloro-
gel; n-hexane/EtOAc, 2:1) gave product 2g (106 mg, 85 %) as a yel-
low oil. H NMR (500 MHz): δ = 10.86 (br.,1 H), 8.74 (d, J = 1.9 Hz,
1
1 H), 8.18 (d, J = 8.7 Hz, 1 H), 7.01 (dd, J = 8.6, 1.9 Hz, 1 H), 2.74 (q,
J = 7.6 Hz, 2 H), 1.38 (s, 9 H), 1.30 (t, J = 7.6 Hz, 3 H) ppm. 13C NMR
form): δ = 169.0, 136.9, 136.2, 133.5, 132.4, 125.5, 122.2, 25.6, 20.6 (101 MHz, [D]Chloroform): δ = 177.7, 139.5, 135.1, 133.2, 128.6,
ppm. MS (EI): m/z (%) = 194 (7) [M+], 167 (55), 149 (100), 113 (21),
83 (14), 71 (31), 57 (33), 43 (18). C9H10N2O3 (194.19): calcd. C 55.67,
H 5.19, N 14.43; found C 55.57, H 5.15, N 14.38.
124.4, 122.1, 40.5, 27.9, 27.5, 15.2 ppm. MS (EI): m/z (%) = 250 (14)
[M+], 204 (18), 166 (30), 151 (37), 85 (27), 71 (21), 57 (100).
C13H18N2O3 (250.29): calcd. C 62.38, H 7.25, N 11.19; found
C 62.49, H 7.29, N 11.24.
N-(5-ethyl-2-nitrophenyl)acetamide (2c): The general procedure
was followed by using 3-Eethylacetanilide (0.5 mmol, 81 mg),
N-(4-methoxy-2-nitrophenyl)pivalamide (2h): The general proce-
NaNO2 (69 mg, 0.5 mmol), K2S2O8 (270 mg, 1.0 mmol), and AgNO2 dure was followed by using 4-methoxylpivanalide (0.5 mmol,
(8 mg, 10 mol-%). Purification by column chromatography (silica 103 mg), NaNO2 (69 mg, 0.5 mmol), K2S2O8 (270 mg, 1.0 mmol),
gel; n-hexane/EtOAc, 2:1) gave product 2c (85 mg, 82 %) as a dark and AgNO2 (8 mg, 10 mol-%). Purification by column chromatogra-
yellow oil. 1H NMR (500 MHz): δ = 10.22 (br., 1 H), 8.66 (d, J = 8.6 Hz,
1 H), 8.04 (d, J = 2.1 Hz, 1 H), 7.50 (dd, J = 8.6, 2.1 Hz, 1 H), 2.71 (q,
J = 7.6 Hz, 2 H), 2.30 (s, 3 H), 1.28 (t, J = 7.6 Hz, 3 H) ppm. 13C NMR
(101 MHz, [D]Chloroform): δ = 169.0, 139.8, 136.4, 135.8, 132.5,
phy (silica gel; n-hexane/EtOAc, 2:1) gave product 2h (112 mg,
89 %) as a yellow oil. H NMR (400 MHz): δ = 10.51 (br., 1 H), 8.73
1
(dd, J = 9.3, 0.6 Hz, 1 H), 7.69 (dd, J = 3.1, 0.6 Hz, 1 H), 7.27–
7.18 (m, 1 H), 3.87 (s, 3 H), 1.37 (s, 9 H) ppm. 13C NMR (101 MHz,
124.3, 122.3, 27.9, 25.6, 15.1 ppm. MS (EI): m/z (%) = 208 (33) [M+], [D]Chloroform): δ = 177.6, 154.7, 136.9, 129.9, 123.7, 123.5, 108.5,
166 (88), 162 (21), 151 (100), 105 (28), 91 (8), 77 (8). C10H12N2O3
(208.21): calcd. C 57.68, H 5.81, N 13.45; found C 57.46, H 5.83, N
13.31.
55.9, 40.4, 27.5 ppm. MS (EI): m/z (%) = 252 (70) [M+], 206 (51), 168
(100), 153 (28), 122 (18), 57 (85), 52 (8). C12H16N2O4 (252.27): calcd.
C 57.13, H 6.39, N 11.10; found C 57.36, H 6.37, N 11.15.
N-(4-hydroxy-2-nitrophenyl)acetamide (2d): The general proce-
N-(4-fluoro-2-nitrophenyl)pivalamide (2i): The general procedure
dure was followed by using 4-hydroxyacetanilide (0.5 mmol, 75 mg),
was followed by using 4-fluoropivalamide (0.5 mmol, 97 mg),
NaNO2 (69 mg, 0.5 mmol), K2S2O8 (270 mg, 1.0 mmol), and AgNO2 NaNO2 (69 mg, 0.5 mmol), K2S2O8 (270 mg, 1.0 mmol), and AgNO2
(8 mg, 10 mol-%). Purification by column chromatography (silica (8 mg, 10 mol-%). Purification by column chromatography (silica
gel; n-hexane/EtOAc, 2:1) gave product 2d (65 mg, 67 %) as a yellow
solid, m.p. 154–155 °C. H NMR (500 MHz): δ = 7.90 (d, J = 2.1 Hz,
gel; n-hexane/EtOAc, 2:1) gave product 2i (82 mg, 69 %) as a dark
yellow solid, m.p. 83–85 °C. H NMR (400 MHz, [D]Chloroform): δ =
1
1
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10.62 (br., 1 H), 8.89 (dd, J = 9.4, 5.2 Hz, 1 H), 7.96 (dd, J = 8.5, 1 H), 8.19 (d, J = 8.6 Hz, 1 H), 7.02 (dd, J = 8.8, 1.8 Hz, 1 H), 2.75 (q,
3.1 Hz, 1 H), 7.56–7.28 (m, 1 H), 1.38 (s, 9 H) ppm. 13C NMR (101 MHz,
J = 7.7 Hz, 2 H), 1.39 (s, 9 H), 1.30 (t, J = 7.6 Hz, 3 H) ppm. 13C NMR
[D]Chloroform): δ = 177.8, 156.8 (d, J = 247.4 Hz), 136.4, 132.0, 124.0 (101 MHz, [D]Chloroform): δ = 178.1, 154.1, 135.6, 134.3, 126.0,
(d, J = 7.1 Hz), 123.5 (d, J = 22.0 Hz), 112.22 (d, J = 27.2 Hz) ppm. 122.8, 121.0, 40.7, 29.4, 27.5, 14.9 ppm. MS (EI): m/z (%) = 250 (33)
MS (EI): m/z (%) = 240 (9) [M+], 149 (18), 118 (35), 98 (25), 85 (17), [M+], 204 (75), 166 (85), 136 (41), 120 (17), 91 (25), 57 (100).
71 (17), 57 (100). C11H13FN2O3 (240.23): calcd. C 55.00, H 5.45, N
11.66; found C 55.17, H 5.50, N 11.73.
C13H18N2O3 (250.29): calcd. C 62.38, H 7.25, N 11.19; found C 52.54,
H 7.23, N 11.11.
N-(4-chloro-2-nitrophenyl)pivalamide (2j): The general procedure
N-(5-chloro-2-nitrophenyl)pivalamide (2o): The general proce-
was followed by using 4-chloropivalamide (0.5 mmol, 106 mg),
dure was followed by using 3-chloropivanalide (0.5 mmol, 105 mg),
NaNO2 (69 mg, 0.5 mmol), K2S2O8 (270 mg, 1.0 mmol), and AgNO2 NaNO2 (69 mg, 0.5 mmol), K2S2O8 (270 mg, 1.0 mmol), and AgNO2
(8 mg, 10 mol-%). Purification by columnchromatography (silica gel; (8 mg, 10 mol-%). Purification by column chromatography (silica
n-hexane/EtOAc, 2:1) gave product 2j (86 mg, 67 %) as a yellow gel; n-hexane/EtOAc, 2:1) gave product 2o (75 mg, 59 %) as a yellow
solid, m.p. 72–74 °C. 1H NMR (400 MHz): δ = 10.67 (br., 1 H), 8.84
(d, J = 9.1 Hz, 1 H), 8.19 (d, J = 2.6 Hz, 1 H), 7.59 (dd, J = 9.2, 2.5 Hz,
1 H), 1.36 (s, 9 H) ppm. 13C NMR (101 MHz, [D]Chloroform): δ =
solid, m.p. 79–81 °C. 1H NMR (500 MHz): δ = 10.86 (br., 1 H), 9.01
(d, J = 2.3 Hz, 1 H), 8.21 (d, J = 9.0 Hz, 1 H), 7.15 (dd, J = 9.1, 2.3 Hz,
1 H), 1.38 (s, 9 H) ppm. 13C NMR (101 MHz, [D]Chloroform): δ =
177.8, 136.3, 135.9, 134.1, 128.0, 125.3, 123.3, 40.6, 27.4 ppm. MS 178.1, 142.9, 136.4, 134.3, 127.0, 123.2, 121.7, 40.7, 27.4 ppm. MS
(EI): m/z (%) = 257 (8) [M + 1], 256 (25) [M+], 172 (31), 85 (43), 57 (EI): m/z (%) = 257 (3) [M + 1], 256 (11) [M+], 210 (32), 172 (48), 85
(100). C11H13ClN2O3 (256.69): calcd. C 51.47, H 5.10, N 10.91; found (23), 57 (100). C11H13ClN2O3 (256.69): calcd. C 51.47, H 5.10, N 10.91;
C 51.33, H 5.12, N 10.96.
found C 51.28, H 5.13, N 10.84.
N-(4-bromo-2-nitrophenyl)pivalamide (2k): The general proce-
N-(4,5-dimethyl-2-nitrophenyl)pivalamide (2p): The general pro-
dure was followed by using 4-Bromopivalamide (0.5 mmol, 127 mg),
cedure was followed by using 3,4-dimethylpivanalide (0.5 mmol,
NaNO2 (69 mg, 0.5 mmol), K2S2O8 (270 mg, 1.0 mmol), and AgNO2 102 mg), NaNO2 (69 mg, 0.5 mmol), K2S2O8 (270 mg, 1.0 mmol),
(8 mg, 10 mol-%). Purification by column chromatography (silica
gel; n-hexane/EtOAc, 2:1) gave product 2k (96 mg, 64 %) as a yellow
solid, m.p. 77–78 °C. 1H NMR (500 MHz): δ = 10.69 (br., 1 H), 8.81
(d, J = 9.2 Hz, 1 H), 8.39 (d, J = 2.5 Hz, 1 H), 7.75 (dd, J = 9.1, 2.4 Hz,
1 H), 1.38 (s, 9 H) ppm. 13C NMR (101 MHz, [D]Chloroform): δ =
and AgNO2 (8 mg, 10 mol-%). Purification by columnchromatogra-
phy (silica gel; n-hexane/EtOAc, 2:1) gave product 2p (101 mg,
81 %) as a yellow solid, m.p. 103–104 °C. 1H NMR (500 MHz): δ =
10.74 (br., 1 H), 8.60 (s, 1 H), 8.05 (s, 1 H), 2.35 (s, 3 H), 2.30 (s, 3 H),
1.38 (s, 9 H) ppm. 13C NMR (101 MHz, [D]Chloroform): δ = 177.9,
177.9, 138.8, 134.6, 132.6, 128.3, 123.6, 115.0, 40.7, 27.4 ppm. MS 147.0, 134.1, 133.3, 132.1, 126.0, 122.6, 40.5, 27.5, 20.5, 19.2 ppm.
(EI): m/z (%) = 301 (18) [M + 1], 300 (18) [M+], 216 (22), 157 (38), 91
(18), 85 (28), 57 (100). C11H13BrN2O3 (301.14): calcd. C 43.87, H 4.35,
N 9.3; found C 43.61, H 4.38, N 9.36.
MS (EI): m/z (%) = 250 (62) [M+], 204 (100), 166 (82), 136 (27), 120
(33), 91 (21), 57 (96). C13H18N2O3 (250.29): calcd. C 62.38, H 7.25, N
11.19; found C 62.18, H 7.29, N 11.26.
N-(2,4-dinitrophenyl)pivalamide (2l): The general procedure was
N-(4,5-dichloro-2-nitrophenyl)pivalamide (2q): The general pro-
followed by using 4-nitropivanalide (0.5 mmol, 112 mg), NaNO2
cedure was followed by using 3,4-dichloropivalamide (0.5 mmol,
(69 mg, 0.5 mmol), K2S2O8 (270 mg, 1.0 mmol), and AgNO2 (8 mg, 123 mg), NaNO2 (69 mg, 0.5 mmol), K2S2O8 (270 mg, 1.0 mmol),
10 mol-%). Purification by column chromatography (silica gel; n-
hexane/EtOAc, 2:1) gave product 2l (76 mg, 57 %) as a yellow solid,
m.p. 107–109 °C. H NMR (500 MHz): δ = 11.05 (br., 1 H), 9.15 (dd,
and AgNO2 (8 mg, 10 mol-%). Purification by column chromatogra-
phy (silica gel; n-hexane/EtOAc, 2:1) gave product 2q (88 mg, 61 %)
1
1
as a yellow solid, m.p. 93–95 °C. H NMR (500 MHz): δ = 10.74 (br.,
J = 6.0, 3.4 Hz, 2 H), 8.48 (dd, J = 9.5, 2.7 Hz, 1 H), 1.39 (s, 9 H) ppm.
1 H), 9.17 (s, 1 H), 8.36 (s, 1 H), 1.38 (s, 9 H) ppm. 13C NMR (101 MHz,
13C NMR (101 MHz, [D]Chloroform): δ = 178.1, 141.5, 140.4, 134.9,
[D]Chloroform): δ = 177.9, 141.2, 134.4, 131.0, 126.8, 126.6, 123.1,
130.1, 122.3, 122.0, 41.0, 27.3 ppm. MS (EI): m/z (%) = 267 (14) [M+], 40.7, 27.4 ppm. MS (EI): m/z (%) = 291 (11) [M+], 253 (23), 191 (22),
168 (54), 149 (9), 118 (33), 98 (18), 85 (38), 57 (100). C11H13N3O5
(267.24): calcd. C 49.44, H 4.90, N 15.72; found C 49.71, H 4.93, N
15.79.
147 (32), 105 (7), 91 (18), 57 (100). C11H12Cl2N2O3 (291.13): calcd. C
45.38, H 4.15, N 9.62; found C 45.29, H 4.18, N 9.66.
N-(4-methyl-2-nitrophenyl)benzamide (2r):[26] The general proce-
dure was followed by using N-(p-tolyl)benzamide (0.5 mmol,
105 mg), NaNO2 (69 mg, 0.5 mmol), K2S2O8 (270 mg, 1.0 mmol),
N-(5-methyl-2-nitrophenyl)pivalamide (2m): The general proce-
dure was followed by using 3-methylace (0.5 mmol, 95 mg), NaNO2
(69 mg, 0.5 mmol), K2S2O8 (270 mg, 1.0 mmol), and AgNO2 (8 mg, and AgNO2 (8 mg, 10 mol-%). Purification by column chromatogra-
10 mol-%). Purification by column chromatography (silica gel; n-
hexane/EtOAc, 2:1) gave product 2m (93 mg, 79 %) as a yellow
solid, m.p. 95–97 °C. H NMR (500 MHz): δ = 10.85 (s, 1 H), 8.71 (s,
phy (silica gel; n-hexane/EtOAc, 2:1) gave product 2r (113 mg, 89 %)
as a yellow solid, m.p. 101–103 °C. 1H NMR (500 MHz, [D]Chloro-
form): δ = 11.26 (br., 1 H), 8.90 (d, J = 8.6 Hz, 1 H), 8.10 (d, J =
2.0 Hz, 1 H), 8.01 (d, J = 7.5 Hz, 2 H), 7.62 (t, J = 7.3 Hz, 1 H), 7.56
(t, J = 7.8 Hz, 2 H), 2.44 (s, 3 H) ppm. 13C NMR (101 MHz, [D]Chloro-
1
1 H), 8.15 (d, J = 8.6 Hz, 1 H), 6.98 (d, J = 7.4 Hz, 1 H), 2.45 (s, 3 H),
1.38 (s, 10 H) ppm. 13C NMR (126 MHz, cdcl3): δ = 178.1, 148.1,
135.4, 134.2, 125.8, 124.0, 122.0, 40.6, 27.5, 22.1 ppm. MS (EI): m/z form): δ = 165.7, 137.9, 137.2, 134.2, 133.7, 133.0, 132.6, 129.1, 127.4,
(%) = 236 (8) [M+], 190 (11), 165 (13), 149 (21), 111 (18), 97 (23), 85
(37), 71 (54), 57 (100). C12H16N2O3 (236.27): calcd. C 61.00, H 6.83,
N 11.86; found C 61.12, H 6.81, N 11.90.
125.7, 122.1, 20.7 ppm. MS (EI): m/z (%) = 256 (22) [M+], 210 (32),
105 (100), 91 (15), 77 (62), 51 (22). C14H12N2O3 (256.26): calcd. C
65.62, H 4.72, N 10.93; found C 65.80, H 4.75, N 10.86.
N-(5-ethyl-2-nitrophenyl)pivalamide (2n): The general procedure
N-(4-methyl-2-nitrophenyl)benzenesulfonamide (2s):[28] The
was followed by using 3-ethylpivalamide (0.5 mmol, 102 mg), general procedure was followed by using N-(p-tolyl)benzenesulfon-
NaNO2 (69 mg, 0.5 mmol), K2S2O8 (270 mg, 1.0 mmol), and AgNO2 amide (0.5 mmol, 130 mg), NaNO2 (69 mg, 0.5 mmol), K2S2O8
(8 mg, 10 mol-%). Purification by column chromatography (silica (270 mg, 1.0 mmol), and AgNO2 (8 mg, 10 mol-%). Purification by
gel; n-hexane/EtOAc, 2:1) gave product 2n (105 mg, 84 %) as a yel-
low oil. H NMR (400 MHz): δ = 10.88 (br., 1 H), 8.75 (d, J = 1.6 Hz,
column chromatography (silica gel; n-hexane/EtOAc, 2:1) gave prod-
1
uct 2s (93 mg, 61 %) as a yellow solid, m.p. 79–80 °C. 1H NMR
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(400 MHz): δ = 9.66 (br., 1 H), 7.90 (s, 1 H), 7.76 (d, J = 8.6 Hz, 1 H),
7.71 (d, J = 8.4 Hz, 2 H), 7.42 (d, J = 8.9 Hz, 2 H), 7.26 (d, J = 8.1 Hz,
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(11), 65 (35), 51 (13). C14H14N2O4S (306.34): calcd. C 54.89, H 4.61,
N 9.14; found C 54.98, H 4.59, N 9.18.
N-(4-methyl-2-nitrophenyl)hexanamide (2t): The general proce-
dure was followed by using N-(p-tolyl)hexanamide (0.5 mmol,
102 mg), NaNO2 (69 mg, 0.5 mmol), K2S2O8 (270 mg, 1.0 mmol),
and AgNO2 (8 mg, 10 mol-%). Purification by column chromatogra-
phy (silica gel; n-hexane/EtOAc, 2:1) gave product 2t (101 mg, 81 %)
as a yellow oil. 1H NMR (400 MHz): δ = 10.48 (br., 1 H), 8.08 (s, 1 H),
7.10 (d, J = 8.4 Hz, 1 H), 6.86 (d, J = 8.6 Hz, 1 H), 2.50 (s, 3 H), 2.37
(t, J = 7.6 Hz, 2 H), 1.67 (p, J = 7.4 Hz, 4 H), 1.34 (q, J = 3.6 Hz, 2 H),
0.92 (t, J = 7.6 Hz, 3 H) ppm. 13C NMR (101 MHz, [D]Chloroform):
δ = 174.0, 143.7, 139.8, 136.1, 129.9, 122.1, 114.5, 34.2, 31.3, 24.6,
22.4, 20.5, 14.0 ppm. MS (EI): m/z (%) = 249 (10) [M+], 167 (42), 149
(100), 118 (29), 71 (53), 57 (72). C13H18N2O3 (250.29): calcd. C 62.38,
H 7.25, N 11.19; found C 62.63, H 7.21, N 11.13.
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Acknowledgments
We gratefully acknowledge the financial support from the Re-
search Council of the University of Tehran and the Iran National
Science Foundation (INSF, no. 96008622). We thank Dr Karol
Gajewski, Natural Resources Canada, for helpful comments on
this work.
Keywords: Anilides · Nitration · Homogeneous catalysis ·
Silver · Synthetic methods
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Received: May 21, 2018
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C–H Functionalization
E. Kianmehr,*
S. Bahrami Nasab .............................. 1–7
Silver-Catalyzed Chemo- and Regio-
selective Nitration of Anilides
A highly regioselective silver-catalyzed sponding ortho-nitroanilides moderate
nitration of anilides through C–H bond to good yields. The reaction proceeds
functionalization produces the corre- with NaNO2 as the nitration agent.
DOI: 10.1002/ejoc.201800779
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© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim