Metal-free C-H Activation over Graphene Oxide toward Direct Syntheses of Structurally Different Amines and Amides in Water

Article abstract of DOI:10.1021/acs.joc.0c02219

Unprecedented metal-free synthesis of a variety of amines and amides is reported via amination of C(sp3)-H and C(sp2)-H bonds. The strategy involves graphene-oxide/I2-catalyzed nitrene insertion using PhINTs as a nitrene (NT) source in water at room temperature. A wide range of structurally different substrates, viz., cyclohexane, cyclic ethers, arenes, alkyl aromatic systems, and aldehydes/ketones, having an α-phenyl ring have been employed successfully to afford the corresponding nitrene insertion product in good yield, albeit low in few cases. The envisaged method has superiority over others in terms of its operational simplicity, metal-free catalysis, use of water as a solvent, ambient reaction conditions, and reusability of the catalyst.

Full text of DOI:10.1021/acs.joc.0c02219

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Article
Metal-free C−H Activation over Graphene Oxide toward Direct
Syntheses of Structurally Different Amines and Amides in Water
Prashant Shukla, Ambika Asati, Smita R. Bhardiya, Manorama Singh, Vijai K. Rai, and Ankita Rai*
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ABSTRACT: Unprecedented metal-free synthesis of a variety of amines and
amides is reported via amination of C(sp3)−H and C(sp2)−H bonds. The
strategy involves graphene-oxide/I2-catalyzed nitrene insertion using PhINTs as
a nitrene (NT) source in water at room temperature. A wide range of structurally
different substrates, viz., cyclohexane, cyclic ethers, arenes, alkyl aromatic
systems, and aldehydes/ketones, having an α-phenyl ring have been employed
successfully to afford the corresponding nitrene insertion product in good yield,
albeit low in few cases. The envisaged method has superiority over others in
terms of its operational simplicity, metal-free catalysis, use of water as a solvent,
ambient reaction conditions, and reusability of the catalyst.
viz., ruthenium(II),18 copper(I),19 and iron(II).20 Although
these reported protocols have many advantages, such as the
use of metals as a catalyst and ligands as a subsidiary catalytic
environment, lower moderate yields, and several byproducts,
the use of hazardous/volatile solvents prevent them from being
considered as environmentally benign methods.
INTRODUCTION
■
Direct transformation of the selective C−H to C−N bond is a
synthetically attractive strategy, which is receiving increasing
attention because of tremendous value of the products amines
and amides in the field of chemistry as well as biology. Since
the seminal work of Breslow,1 N-tosylation has been one of the
most interesting reactions for direct C−N bond formation
through nitrene insertion into the C−H bond of structurally
divergent substrates.2 Direct C(sp3)−H amination of ethers,
cyclic ethers, hydrocarbons, and so forth using Mn,3 Ru,4 and
Cu5−7 catalysts is well-documented.3−7 Similarly, CoII-,8
gold(III)-,9 and Cu10-catalyzed amination of the benzylic
C(sp3)−H bond has also been reported either by nitrene
insertion or via C−N coupling.8−10 Besides, intramolecular C−
H amination via activation of C(sp3)−H and C(sp2)−H bonds
toward synthesis of heterocyclic scaffolds has also been well-
documented.11,12
The literature records several reports on amination of the
C(sp2)−H bond of benzene2,9,12−17 and carbonyls18−20 to
generate the corresponding aromatic amines and amides,
respectively. Most of the best-established amination ap-
proaches are reported through metal-catalyzed formal insertion
of the nitrene group from iminoiodanes (PhINR; R = Ts,
Ns) into the C(sp2)−H bond of benzene.2,9,12,15,16 In this
regard, AuCl3-promoted nitrene insertion9 and Fe2b/Cu−
homoscorpionate complex15,16-catalyzed generation of nitrene
from PhINTs have been utilized for amination of the
C(sp2)−H bond. This is also reported by metal-catalyzed
reactions with diethylamine/ammonia13,14 and via N-aryla-
tion17 strategies. Furthermore, C(sp2)−H amidation of
aldehydes has also been reported using metal catalysts,18−20
Recently, metal-free C−H amination of arene has been
reported; however, substrate scope is limited to the aromatic
C(sp2)−H bond.21a Furthermore, graphene oxide (GO)-
catalyzed C−N coupling21b and C−H activations21c−e have
been reported, but the use of GO toward activation of C(sp3)−
H and C(sp2)−H bonds for amination has not been explored
so far. To bridge this literature gap and in continuation of our
research program,22 especially on C−H activation,23 we herein
disclosed a metal-free carbocatalytic direct amination of
structurally different substrates, viz., cyclohexane, cyclic ethers,
arenes, alkyl aromatic systems, and aldehydes/ketones, having
an α-phenyl ring in water using PhINTs as a nitrene precursor
(Scheme 1). The novelty and superiority of the present work
over previously reported ones lies in the regioselective
formation of structurally different protected amines and
amides and minimizing the byproduct formation during the
course of reaction.
Received: September 24, 2020
https://dx.doi.org/10.1021/acs.joc.0c02219
© XXXX American Chemical Society
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Scheme 1. C(sp3)−H and C(sp2)−H Activation for
water was the best choice as a solvent in the present
optimization protocol perhaps because of fair dispersion of
GO in water. However, increasing the amount of GO as well as
I2 did not increase the yield, while on decreasing their amount,
lower yield of target aniline derivative 3a was obtained (Table
1, entries 10−13). Just to compare the catalytic efficiency,
graphite and reduced GO were also screened but were found
ineffective as a catalyst as we did not isolate any product
(Table 1, entries 2, 3). The reaction was not successful either
in the absence of GO (Table 1, entry 14) or in the absence of
I2 (Table 1, entry 15). Thus, 20 mg of GO and 0.05 mmol I2
were found to be the optimized catalyst loading for the present
conversion in water at room temperature.
Synthesis of Amides and Aliphatic/Aromatic Amines
RESULTS AND DISCUSSION
After functionalization of the C−H bond of benzene, various
substituted benzenes with electron-withdrawing and electron-
releasing groups were utilized for C−H amination (Table 2).
■
At the outset, we decided to explore the catalytic capabilities of
GO as a carbocatalyst for amination of the C−H bond. First,
the reaction conditions were optimized taking benzene 1a as a
model substrate with different solvents (Table 1). We have
a
Table 2. C(sp2)−H Activation for Amination of Arenes
Table 1. Optimization of Reaction Conditions for C−H
a
Amination of Benzene 1a
b
cd
,
s. no. catalyst (mg) I2 (mmol)
solvent
time (h)
yield (%)
55
1
2
3
4
5
6
7
8
GO (20)
graphite (20)
r-GO (20)
GO (20)
GO (20)
GO (20)
GO (20)
GO (20)
GO (20)
GO (30)
GO (15)
GO (20)
GO (20)
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.10
0.025
0.10
H2O
H2O
H2O
MeOH
EtOH
DCM
EtOAc
n-hexane
Et2O
H2O
25
35
35
25
25
25
25
30
30
28
28
28
28
28
30
49
45
37
42
a
Reaction condition: a mixture of I2 (0.05 mmol), PhINTs (0.5
mmol), GO (20 mg), and 1 (2 mmol) in water (5 mL) was stirred at
room temperature for 25 h. All compounds are characterized by their
satisfactory spectral (IR, 1H NMR, 13C NMR, and HRMS) data
(ESI).
9
10
11
12
13
14
15
55
33
55
30
00
H2O
H2O
H2O
H2O
However, conversion into target amine was lower than that for
benzene in the case of electron-releasing groups, aniline (Table
2, 3d), while yield of 3 was improved in the case of electron-
withdrawing groups (Table 2, 3b, 3c). Surprisingly, we did not
isolate the corresponding aminated products under the same
reaction conditions using p-chloroaniline (1e) and pyridine
(1f) as substrates. Presumably, high electron density due to the
N-atom with a lone pair of electrons in 1e and counter-
attacking deactivating groups in 1f is responsible for
deactivating the ring H-atom. Thus, we have successfully
achieved a metal-free carbocatalytic nitrene unit NT insertion
from PhINTs into several aromatic compounds using green
chemistry protocol. However, TsNH2 was formed as a
byproduct in all the cases. The reason for the p-tolyl group
of the TsNH2 byproduct not getting aminated is presumably
the complete consumption of generated nitrene by the
substrate before the formation of tosylamine as a byproduct.
For general validity of the process, the optimized reaction
condition was successfully employed for amination of alkyl
aromatic compound, cyclohexane, and cyclic ethers containing
primary and secondary alkyl C(sp3)−H bonds (Table 3).
Structurally different alkyl aromatic compounds (Table 3, 4a−
4d) were chosen, and the reactions were performed at room
temperature, PhINTs was completely consumed as monitored
GO (20)
H2O
00
a
b
2 mmol benzene 1a and 0.5 mmol PhINTs 2 were used. Stirring
c
time at room temperature. Yield of isolated and purified compound
d
3a. Compound 3a was characterized by satisfactory spectral (1H
NMR, 13C NMR, and HRMS) data (ESI).
chosen GO and iodine to carry out preliminary experimenta-
tion for nitrene insertion using PhINTs.24 The reaction was
performed by taking a mixture of I2 (0.05 mmol), PhINTs (0.5
mmol), GO (20 mg), and benzene (2 mmol) in 5 mL of water
and the reaction mixture was stirred at room temperature. To
our surprise, the reaction was completed in 25 h (Table 1,
entry 1) and we were delighted to obtain the desired product
3a along with TsNH2 as a byproduct. The corresponding
aniline derivative 3a was isolated in 55% yield, with respect to
the amount of the initial nitrene source, the remaining being
converted into TsNH2 because of aqueous medium. We next
tried different polar protic solvents such as MeOH and EtOH
(Table 1, entries 4, 5) but lower yield of aniline derivative 3a
was obtained. Polar aprotic solvents were also not effective as
water (Table 1, entries 6, 7), while the present conversion was
not observed in nonpolar solvents (Table 1, entries 8, 9). Thus,
B
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Table 3. C(sp3)−H Activation for Amination of Alkyl
Table 4. Amination of Alkyl C(sp3)−H Attached to the
a
a
Arenes, Cyclic Ethers, and Cycloalkane
Carbonyl Group of 6
a
Reaction condition: a mixture of I2 (0.05 mmol), PhINTs (0.5
mmol), GO (20 mg), and 6 (2 mmol) in water (5 mL) was stirred at
room temperature for 25 h. All compounds are characterized by their
satisfactory spectral (IR, 1H NMR, 13C NMR, and HRMS) data
(ESI).
a
Reaction condition: a mixture of I2 (0.05 mmol), PhINTs (0.5
mmol), GO (20 mg), and 4 (2 mmol) in water (5 mL) was stirred at
room temperature for 25 h. All compounds are characterized by their
satisfactory spectral (IR, 1H NMR, 13C NMR, and HRMS) data
(ESI).
other was TsNH2 as a byproduct. However, in the case of
aliphatic aldehyde 8a, relatively lower yield was obtained and
four products were isolated with major nitrene insertion
product 9a, along with TsNH2 and the remaining two were
nitrene insertion at 1° and 2° alkyl carbon of the side chain of
aliphatic aldehyde (Table 5). The electronic effect of
substituents at the phenyl ring affected the conversion rate
substantially; aldehyde 8 with EWG afforded excellent yields of
the corresponding amide 9, while those with electron-releasing
groups resulted in decrease in the yield (Table 5).
Furthermore, the potential utility of the envisaged synthetic
protocol for gram-scale synthesis of 3a was also investigated by
setting a model reaction using 17 times amount of each
substrate utilized in the optimized reaction condition (Table
1). The reaction afforded 1.09 g of the desired product 3a in
52% yield without any significant loss of its efficiency, thus
demonstrating the potential application of the protocol for a
large-scale synthesis of the target compound. Thus, we have
successfully achieved the C−H amination of the structurally
different substrate in good-to-excellent yield, albeit low yield in
some cases. However, insolubility of the PhINTs and
generation of p-toluenesulfonamide in aqueous medium are
the probable reasons for lower yield, which is also supported
by the literature.15 Moreover, oxygen functionalities on GO
make it hydrophilic and this was the big reason to take water as
a solvent in addition to its green credentials. GO is well-
dispersed in water by which its surface area is increased and
carboxylic groups present on the surface of GO, along with
iodine, synergistically catalyze the generation of N,N-
diiodotosylamide 10.
by thin layer chromatography (TLC). In the case of toluene
and xylene, slightly lower yield of the corresponding product
was reported (Table 3, 5a, 5b). However, alkyl arenes with
EWG at the alkyl group (4c, 4d) were found to afford better
conversion (Table 3, 5c, 5d). Amination of cyclohexane has
been well-studied in the literature through formal NT insertion
into the C(sp3)−H bond; however, the reported conversion
rate is very slow.17,19 Using this catalytic system, we also
obtained only 56% of the corresponding amine (Table 3, 5f),
perhaps remainder being converted into TsNH2 because of the
presence of water.17,19 We next explored the present reaction
condition for five- and six-membered rings containing
heteroatoms, that is, cyclic ethers (Table 3, 4e, 4g), and
found that the C−H bond at α-carbon vicinal to oxygen was a
selective site for nitrene insertion.19,25,26 Surprisingly, we
obtained the corresponding insertion product of tetrahydrofur-
an and 1,4-dioxane in appreciable yield: 74% of 5e and 76% of
5g, respectively (Table 3).
After successful amination of the alkyl group attached to
benzene (sp2-C) through C(sp3)−H activation, we wished to
undertake amination of the alkyl group attached to carbonyl
carbon (sp2-C). Thus, a variety of acetophenones (6a−f)
bearing different substituents at the phenyl ring were explored
and surprisingly the corresponding amines (7a−f) were
obtained in good to satisfactory yield (Table 4). Synthesis of
amides is important in many areas of chemistry, including
peptide, polymer, and complex molecule synthesis.27,28 Keep-
ing this in mind, we next employed these optimized reaction
conditions also for synthesis of amides. Thus, a mixture of
benzaldehyde 8c, PhINTs 2, I2, and GO was stirred in water at
room temperature and we were happy to see two new spots
after 25 h and PhINTs were completely consumed. In the case
of benzaldehyde derivatives, we obtained two products; one
which was the expected nitrene insertion product 9, while the
Formation of C−H amination has been explained by a
plausible mechanism given in Scheme 2 on the basis of
controlled experiments performed and relevant literature
reports involving amidyl radical species.24b Initially, I2 reacted
with GO-activated PhINTs to produce N,N-diiodotosylamide
10 followed by generation of amidyl radical 11 because of the
labile nature of homolytic cleavage of the N−I bond.24a The
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Table 5. Substrate Scope for C(sp2)−H Amination for
the presence of amidyl radical 11, which was quenched with
TEMPO leading to the new product in the reaction mixture
(observed in TLC). Presumably, amidyl radical 11 undergoes
radical induced-nitrene insertion into the C−H bond to afford
the desired C−H amination and is the cornerstone of the
reaction. Furthermore, the iodine radical formed with 11 and
that in the final amination step recombined to reproduce I2,
which would be reused in the next catalytic cycle.
a
Synthesis of Amide 9
Furthermore, a control experiment was performed just to
investigate the generation of amidyl radical 11 through N,N-
diiodotosylamide 10 and also to observe the catalytic role of
GO and iodine in the present investigation. Thus, a mixture of
I2 (0.05 mmol), PhINTs (0.5 mmol), GO (20 mg), and
TEMPO (0.5 mmol) in 5 mL of water was stirred at room
temperature. After 25 h of stirring, we isolated N-iodo-4-
methyl-N-((2,2,6,6-tetramethylpiperidin-1-yl)oxy)-
benzenesulfonamide (X). The structure of X was confirmed by
its HRMS and elemental analyses.31 The catalytic system
(GO/I2) evidenced its efficiency to produce the intermediate
X having the N−I bond, in spite of its labile nature. However,
we could not isolate the other possible intermediates Y and Z
(Scheme 3). This might be due to steric hindrance, and
Scheme 3. Trapping of the Intermediate Radical with
TEMPO
a
Reaction condition: a mixture of I2 (0.05 mmol), PhINTs (0.5
mmol), GO (20 mg), and 8 (2 mmol) in water (5 mL) was stirred at
room temperature for 25 h. All compounds are characterized by their
satisfactory spectral (IR, 1H NMR, 13C NMR, and HRMS) data
(ESI).
because of the absence of other suitable free radicals, iodine
remains attached with product X. Other control experiments
were also performed to decide the role of each of the GO and
iodine as well toward the formation of intermediate X in the
present protocol. By stirring a mixture of PhINTs (0.5 mmol)
and TEMPO (0.5 mmol) in 5 mL of water at room
temperature, in the absence of either GO or I2, we did not
isolate the intermediate X even after 30 h. Similarly,
intermediate X was not formed, when a reaction was run by
stirring a mixture of I2 (0.05 mmol), PhINTs (0.5 mmol), and
TEMPO (0.5 mmol) in 5 mL of water at room temperature in
the presence of either graphite (20 mg) or r-GO (20 mg) as a
catalyst. These experiments concluded us the presence of both;
GO and I2 are essential for the C−H activation, presumably
iodine and the oxygen functionalities on the surface of GO
helped in generation of amidyl radical 11. The reusability
(Figure 1) of the GO as a heterogeneous catalyst was also
examined for the formation of aniline derivative 3a and was
recovered from the first batch of reaction by centrifugation
followed by washing and drying and then it was reused for
subsequent next batches of reactions (Figure 1). Appreciable
conversions were achieved in all recycling experiments carried
out at room temperature. Comparison of the X-ray diffraction
(XRD) (Figure 2a) and Fourier transform infrared (FT-IR)
spectra (Figure 2b) of the GO before and after use of the fifth
batch confirmed the stability of the catalyst after completion of
the reaction (Figure 2).
Scheme 2. Plausible Mechanism for C−H Amination
formation of amidyl radical 11 was confirmed by trapping it
with TEMPO. After adding TEMPO in the reaction mixture,
only one spot, different from that of the product, was observed
in TLC, while no other spot corresponding to the substrate
and TEMPO was noticed. This observation led us to resolute
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Figure 3. (a) SEM of GO and (b) HR-TEM of GO. Inset: diffraction
pattern of GO.
These attributes make the envisaged protocol as highly green
and would be an improved practical alternative method for
synthesis of such a type of fine chemicals to cater the need of
academia as well as industry.
Figure 1. Reusability experiment of the catalyst used for the formation
of 3a.
EXPERIMENTAL SECTION
■
The GO was prepared by its reported method,29 and its
structure was confirmed by XRD, FT-IR, scanning electron
microscopy (SEM), and transmission electron microscopy
(TEM) along with comparison with literature reports.30 XRD
shows a strong and sharp peak at 2θ = 9.96° (002), which
clearly indicates the structure of prepared GO. The interlayer
spacing was found to be 0.89 nm (Figure 2a). The presence of
different oxygen-containing functional groups was confirmed
by FT-IR (Figure 2b), such as a peak at 3100−3450 cm−1 for
the −OH (hydroxyl) group and 1717 cm−1 for −COO−
(carboxyl) groups in GO layers. Peaks at 1238.6 cm−1 (C−
O str) and 1058.08 cm−1 (C−O str) confirmed the presence of
epoxy groups. Oxidation of graphite exfoliated the layers and
introduces several oxygen moieties in the basal plane of GO
(SEM, Figure 3a). A wrinkled and thick surface of few-layered
morphology of GO was observed in high-resolution (HR)
TEM (Figure 3b). Crystallinity of the layer was recorded by
selected area electron diffraction (inset, Figure 3b).
In conclusion, we have disclosed a green and facile route for
introducing the NT group into the C−H bond of arenes, alkyl
arenes, aromatic ketones, cyclohexane, cyclic ethers, and
aliphatic as well as aromatic aldehydes under ambient reaction
conditions using water as a solvent. The envisaged method
involves metal-free nitrene insertion using GO as a
carbocatalyst and PhINTs as a nitrene source to afford a
variety of amines and amides in moderate-to-good yields.
General Information. Reagents were obtained from commercial
suppliers and used without further purification unless otherwise
specified by a reference. All reactions were performed using oven-
dried glassware under a nitrogen atmosphere. Organic solutions were
concentrated using a Buchi rotary evaporator. Column chromatog-
raphy was carried out over silica gel (Merck 60−120 mesh) and TLC
was performed using silica gel GF254 (Merck) plates. IR spectra in
KBr were recorded on a Shimadzu 400−4000 cm−1 FT-IR
spectrophotometer, 1H NMR spectra were recorded on a Bruker
AVIII 500 spectrometer in CDCl3, and dimethyl sulfoxide (DMSO)
with a chemical shift value was reported in ppm. All coupling
constants (J) are reported in Hertz (Hz). 13C NMR spectra were
recorded on the same instrument at 125 MHz in CDCl3. Elemental
analyses were carried out in a Coleman automatic carbon, hydrogen,
and nitrogen analyzer.
General Procedure for the Synthesis of Amines/Amides. In
a mixture of iodine (0.05 mmol), PhINTs (0.5 mmol), and GO (20
mg) in 5 mL of distilled water was added the aldehyde/acetophenone
derivative/cyclic aromatic or aliphatic derivative (2 mmol). The
mixture was stirred at room temperature for 25 h. After completion of
the reaction (as monitored by TLC, 30% EtOAc/hexane), a saturated
solution of sodium thiosulfate was added to the reaction mixture
followed by simple filtration and washing of the residue (GO) using
diethyl ether (5 mL × 3). The catalyst was then washed with water
and ethanol, dried under vacuum, and reused for further experiment.
Then, the reaction mixture was washed sequentially with diethyl ether
(10 mL × 3) and water (10 mL × 2). The combined organic extracts
were dried over K2CO3 and concentrated under reduced pressure to
obtain the crude product, which was purified by column
Figure 2. (a) XRD and (b) FT-IR of GO before and after use.
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chromatography to afford analytically pure samples 3, 5, 7, and 9. All
the synthesized compounds are known (except 3c and 5d) and their
spectral data are in well-agreement with those reported in the
literature.32−34 However, the structure of all the products 3, 5, 7, and
9 was confirmed by their elemental and spectral analysis.
(ESI): calcd for C14H15NO2S, [M+] 261.0823; found, 261.0826. Anal.
Calcd for C14H15NO2S: C, 64.34; H, 5.79; N, 5.36. Found: C, 64.05;
H, 6.04; N, 5.09.
p-Tolyl-N-tosylmethanamine (5b).32d Eluent in chromatography:
n-hexane/EtOAc 97:3. Yellow crystalline solid, yield 55 mg, 40%. mp
90−92 °C. IR (KBr): (ν) 3260, 2927, 1590, 1487, 1455, 1322, 1154,
1081, 1055 cm−1. 1H NMR (CDCl3, 500 MHz): δ 7.55 (d, 2H, J = 8.5
Hz), 7.25 (d, 2H, J = 8.0 Hz), 7.12 (d, 2H, J = 8.5 Hz), 7.03 (d, 2H, J
= 8.0 Hz), 4.40 (t, 1H, J = 6.0 Hz), 4.03 (d, 2H, J = 6.0 Hz), 2.38 (s,
3H), 2.33 (s, 3H). 13C{1H} NMR (CDCl3, 125 MHz): δ 143.3,
142.1, 137.7, 136.3, 129.6, 128.7, 127.3, 126.3, 45.6, 21.7, 21.6.
HRMS (ESI): calcd for C15H17NO2S, [M+] 275.0980; found,
275.0982. Anal. Calcd for C15H17NO2S: C, 65.43; H, 6.22; N, 5.09.
Found: C, 65.66; H, 6.53; N, 4.89.
Typical Procedure for Synthesis of Compound 3a on Gram
Scale. In a mixture of iodine (0.85 mmol), PhINTs (8.5 mmol), and
GO (340 mg) in 45 mL of distilled water was added 1a (34 mmol).
The mixture was stirred at room temperature for 25 h. After
completion of the reaction (as monitored by TLC, 30% EtOAc/
hexane), a saturated solution of sodium thiosulfate was added to the
reaction mixture followed by simple filtration and washing of the
residue (GO) using diethyl ether (10 mL × 3). The catalyst was then
washed with water and ethanol, dried under vacuum, and reused for
further experiment. Then, the reaction mixture was washed
sequentially with diethyl ether (20 mL × 3) and water (15 mL ×
2). The combined organic extracts were dried over K2CO3 and
concentrated under reduced pressure to obtain the crude product,
which was purified by column chromatography to afford an
analytically pure product 3a (1.088 g, 52% yield) as a white solid.
N-Tosylbenzenamine (3a).32a Eluent in chromatography: n-
hexane/EtOAc 97:3. White solid, yield 68 mg, 55%. mp 103−104
°C. IR (KBr): (ν) 3244, 1591, 1479, 1405, 1330, 1284, 1158, 1093,
918, 754, 691, 658, 560, 544, 424 cm−1. 1H NMR (CDCl3, 500
MHz): δ 7.73−7.75 (m, 2H), 7.70 (d, 2H, J = 8.0 Hz), 7.64−7.67 (m,
2H), 7.45−7.49 (m, 1H), 7.25 (d, 2H, J = 8.0 Hz), 4.00 (br s, 1H),
2.37 (s, 3H). 13C{1H} NMR (125 MHz; CDCl3): δ 143.7, 136.9,
136.4, 129.9, 129.7, 127.4, 124.2, 121.7, 21.2. HRMS (ESI): calcd for
C13H13NO2S, [M+] 247.0667; found, 247.0664. Anal. Calcd for
C13H13NO2S: C, 63.13; H, 5.30; N, 5.66. Found: C, 62.91; H, 5.04;
N, 5.97.
Phenyl(tosylamino)methanol (5c).32e Eluent in chromatography:
n-hexane/EtOAc 24:1. Pale yellow liquid, yield 87 mg, 63%. IR
(KBr): (ν) 3343, 3260, 1592, 1489, 1452, 1322, 1163, 1082 cm−1. 1H
NMR (CDCl3, 500 MHz): δ 7.99 (d, 2H, J = 7.5 Hz), 7.98 (s, 1H),
7.36 (d, 2H, J = 7.5 Hz), 7.22−7.33 (m, 5H), 5.27 (s, 1H), 4.70 (s,
1H), 2.20 (s, 3H). 13C{1H} NMR (CDCl3, 125 MHz): δ 141.7,
137.9, 136.1, 129.8, 128.7, 128.5, 128.3, 128.1, 77.8, 21.6. HRMS
(ESI): calcd for C14H15NO3S, [M+] 277.0772; found, 277.0770. Anal.
Calcd for C14H15NO3S: C, 60.63; H, 5.45; N, 5.05. Found: C, 60.40;
H, 5.66; N, 5.35.
Chloro(phenyl)-N-tosylmethanamine (5d). Eluent in chromatog-
raphy: n-hexane/EtOAc 97:3. Reddish viscous oil, yield 90 mg, 61%.
IR (KBr): (ν) 3254, 1593, 1489, 1453, 1320, 1160, 1080, 1053, 655
1
cm−1. H NMR (DMSO, 500 MHz): δ 7.70 (d, 2H, J = 8.0 Hz),
7.26−7.38 (7H, m), 4.48 (s, 1H), 4.38 (br s, 1H), 2.36 (s, 3H).
13C{1H} NMR (DMSO, 125 MHz): δ 142.0, 137.9, 136.7, 130.1,
129.4, 128.2, 127.7, 127.6, 68.6, 21.1. HRMS (ESI): calcd for
C14H14ClNO2S, [M+] 295.0433; found, 295.0432. Anal. Calcd for
C14H14ClNO2S: C, 56.85; H, 4.77; N, 4.74. Found: C, 57.17; H, 4.47;
N, 4.51.
2-Tosylbenzenamine (3b).32b Eluent in chromatography: n-
hexane/EtOAc 24:1. White solid, yield 119 mg, 77%. mp 116−117
°C. IR (KBr): (ν) 3270, 1682, 1591, 1574, 1487, 1455, 1398, 1341,
1288, 1194, 1154, 1082 cm−1. 1H NMR (CDCl3, 500 MHz): δ 11.77
(br s, 1H), 8.09 (d, 1H, J = 7.5 Hz), 7.69−7.76 (m, 3H), 7.57 (t, 1H,
J = 7.0 Hz), 7.44 (d, 2H, J = 7.5 Hz), 7.27 (t, 1H, J = 7.5 Hz), 2.38 (s,
3H); 13C{1H} NMR (CDCl3, 125 MHz): δ 172.7, 144.9, 140.3,
136.4, 135.8, 134.0, 130.4, 128.7, 123.4, 119.8, 119.4, 21.9. HRMS
(ESI): calcd for C14H12ClNO3S, [M+] 309.0226; found, 309.0224.
Anal. Calcd for C14H12ClNO3S: C, 54.28; H, 3.90; N, 4.52. Found: C,
54.55; H, 3.58; N, 4.83.
Tetrahydro-N-tosylfuran-2-amine (5e).32f Eluent in chromatog-
raphy: n-hexane/EtOAc 24:1. White solid, yield 89 mg, 74%. mp
1
123−124 °C. IR (KBr): (ν) 3274, 1732, 1260, 729, 628 cm−1. H
NMR (CDCl3, 500 MHz): δ 7.58 (d, 2H, J = 8.0 Hz), 7.25 (d, 2H, J =
8.0 Hz), 5.83 (s, 1H), 4.84−4.96 (m, 1H), 3.57−3.60 (m, 2H), 2.30
(s, 3H), 1.81−1.85 (m, 1H), 1.61−1.68 (m, 3H). 13C{1H} NMR
(CDCl3, 125 MHz): δ 143.4, 137.5, 130.3, 127.6, 85.1, 67.3, 32.9,
24.0, 21.7. HRMS (ESI): calcd for C11H15NO3S, [M+] 241.0772;
found, 241.0780. Anal. Calcd for C11H15NO3S: C, 54.75; H, 6.27; N,
5.80. Found: C, 55.07; H, 6.48; N, 5.60.
N-(5-Chloro-2-sulfamoylphenyl)-4-methylbenzenesulfonamide
(3c). Eluent in chromatography: n-hexane/EtOAc 24:1. Yellowish
viscous oil, yield 111 mg, 62%. IR (KBr): (ν) 3332, 3260, 3240, 1570,
N-Tosylcyclohexanamine (5f).32g Eluent in chromatography: n-
hexane/EtOAc 97:3. White solid, yield 44 mg, 56%. mp 83−85 °C. IR
(KBr): (ν) 3276, 2929, 2550, 1446, 1320, 1154, 1080 cm−1. 1H NMR
(CDCl3, 500 MHz): δ 7.75 (d, 2H, J = 7.5 Hz) 7.26 (d, 2H, J = 7.5
Hz), 4.66 (br s, 1H), 4.23−4.26 (m, 1H), 2.38 (s, 3H), 2.28−2.31 (m,
2H), 1.95−2.00 (m, 3H), 0.77−0.83 (m, 5H). 13C{1H} NMR
(CDCl3, 125 MHz): δ 143.7, 138.5, 129.2, 127.7, 52.1, 33.4, 25.4,
25.0, 21.9. HRMS (ESI): calcd for C13H19NO2S, [M+] 253.1136;
found, 253.1139. Anal. Calcd for C13H19NO2S: C, 61.63; H, 7.56; N,
5.53. Found: C, 61.96; H, 7.25; N, 5.32.
1
1472, 1330, 1320, 1153, 1150, 1089, 822, 750, 624 cm−1. H NMR
(CDCl3, 500 MHz): δ 10.06 (s, 1H), 7.97−8.05 (m, 3H), 7.47 (d,
2H, J = 8.0 Hz), 7.29 (s, 1H), 7.06 (d, 1H, J = 8.5 Hz), 4.91 (br s,
2H), 2.41 (s, 3H); 13C{1H}NMR (CDCl3, 125 MHz): δ 147.3, 138.7,
138.6, 131.1, 130.4, 129.0, 127.4, 124.7, 124.2, 119.3, 22.9; HRMS
(ESI): calcd for C13H13ClN2O4S2, [M+] 360.0005; found, 360.0003.
Anal. Calcd for C13H13ClN2O4S2: C, 43.27; H, 3.63; N, 7.76. Found:
C, 43.57; H, 3.87; N, 7.56.
N-Tosylbenzene-1,3-diamine (3d).32c Eluent in chromatography:
n-hexane/EtOAc 24:1. Brown solid, yield 48 mg, 37%. mp 143−144
°C. IR (KBr): (ν) 3480, 3398, 3259, 1612, 1590, 1498, 1408, 1304,
1148, 1088 cm−1. 1H NMR (CDCl3, 500 MHz): δ 8.61 (s, 1H), 7.47
(d, 2H, J = 8.0 Hz), 7.27 (d, 2H, J = 8.0 Hz), 6.89−7.00 (m, 3H),
6.12 (d, 1H, J = 8.0 Hz), 5.29 (br s, 2H), 2.12 (s, 3H). 13C{1H} NMR
(CDCl3, 125 MHz): δ 149.9, 142.8, 138.4, 137.1, 129.5, 129.2, 126.7,
109.9, 107.6, 105.4, 20.9. HRMS (ESI): calcd for C13H14N2O2S, [M+]
262.0776; found, 262.0781. Anal. Calcd for C13H14N2O2S: C, 59.52;
H, 5.38; N, 10.68. Found: C, 59.82; H, 5.12; N, 10.48.
N-Tosyl-1,4-dioxan-2-amine (5g).32h Eluent in chromatography:
n-hexane/EtOAc 24:1. White solid, yield 97 mg, 76%. mp 129−130
1
°C. (KBr): (ν) 3273, 2940, 1720, 1161, 1156, 1032, 630 cm−1. H
NMR (CDCl3, 500 MHz): δ 7.87 (d, 2H, J = 8.5 Hz), 7.47 (d, 2H, J =
8.5 Hz), 5.24 (s, 1H), 4.89 (br s, 1H), 4.23−4.26 (m, 3H), 3.57−3.61
(m, 3H), 2.39 (s, 3H). 13C{1H} NMR (CDCl3, 125 MHz): δ 143.3,
138.7, 129.0, 127.4, 78.3, 70.3, 65.8, 62.7, 22.9. HRMS (ESI): calcd
for C11H15NO4S, [M+] 257.0721; found, 257.0725. Anal. Calcd for
C11H15NO4S: C, 51.35; H, 5.88; N, 5.44. Found: C, 51.55; H, 5.56;
N, 5.74.
Phenyl-N-tosylmethanamine (5a).32a Eluent in chromatography:
n-hexane/EtOAc 97:3. White solid, yield 59 mg, 45%. mp 112−113
°C. IR (KBr): (ν) 3264, 1592, 1489, 1453, 1320, 1160, 1085, 1052
cm−1. 1H NMR (CDCl3, 500 MHz): δ 7.71 (d, 2H, J = 8.5 Hz), 7.37
(d, 2H, J = 8.5 Hz), 7.23−7.30 (m, 5H), 4.55 (br s, 1H), 4.06 (d, 2H,
J = 6.0 Hz), 2.38 (s, 3H). 13C{1H} NMR (CDCl3, 125 MHz): δ 144.8
137.2, 136.4, 129.9, 129.7, 128.9, 128.6, 127.4, 47.5, 21.7. HRMS
N-(2-Oxo-2-phenylethyl)-4-methylbenzenesulfonamide (7a).33a
Eluent in chromatography: n-hexane/EtOAc 24:1. White solid, yield
80 mg, 56%. mp 121−124 °C. IR (KBr): (ν) 3278, 2920, 2850, 1686,
1594, 1581, 1492, 1448, 1410, 1343, 1324, 1230, 1180, 1155, 1093,
1020, 980, 928, 815, 755, 670, 652, 542 cm−1. 1H NMR (DMSO, 500
MHz): δ 8.33 (d, 2H, J = 9.0 Hz), 7.73 (d, 2H, J = 8.0 Hz), 7.54−7.58
F
https://dx.doi.org/10.1021/acs.joc.0c02219
J. Org. Chem. XXXX, XXX, XXX−XXX

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pubs.acs.org/joc
Article
(m, 2H), 7.33−7.38 (m, 1H), 7.16−7.22 (m, 2H), 5.75 (br s, 1H),
4.44 (d, 2H, J = 4.5 Hz), 2.37 (s, 3H). 13C{1H} NMR (DMSO, 125
MHz): δ 192.6, 142.7, 135.3, 134.8, 133.4, 129.4, 129.0, 128.3, 127.5,
48.6, 21.1. HRMS (ESI): calcd for C15H15NO3S, [M+] 289.0772;
found, 289.0768. Anal. Calcd for C15H15NO3S: C, 62.26; H, 5.23; N,
4.84. Found: C, 61.97; H, 5.53; N, 5.15.
N-(2-(4-Cholorophenyl)-2-oxoethyl)-4-methylbenzenesulfona-
mide (7b).33b Eluent in chromatography: n-hexane/EtOAc 24:1.
White solid, yield 109 mg, 68%. mp 153−155 °C. IR (KBr): (ν) 3282,
2926, 1681, 1603, 1447, 1333, 1153, 1098, 980, 812, 753, 742, 671,
552 cm−1. 1H NMR (CDCl3, 500 MHz): δ 7.81 (d, 2H, J = 8.0 Hz),
7.43 (d, 2H, J = 8.0 Hz), 7.39 (d, 2H, J = 8.0 Hz), 7.23 (d, 2H, J = 8.5
Hz), 5.56 (br s, 1H), 4.36 (d, 2H, J = 4.5 Hz), 2.34 (s, 3H). 13C{1H}
NMR (CDCl3, 125 MHz): δ 197.5, 141.0, 140.5, 135.2, 131.8, 129.4,
129.3, 129.1, 127.4, 48.8, 22.9. HRMS (ESI): calcd for
C15H14ClNO3S, [M+] 323.0382; found, 323.0381. Anal. Calcd for
C15H14ClNO3S: C, 55.64; H, 4.36; N, 4.33. Found: C, 55.37; H, 4.58;
N, 4.08.
N-(2-(4-Bromophenyl)-2-oxoethyl)-4-methylbenzenesulfona-
mide (7c).33b Eluent in chromatography: n-hexane/EtOAc 24:1.
White solid, yield 117 mg, 64%. mp 121−123 °C. IR (KBr): (ν) 3284,
2927, 1684, 1596, 1449, 1341, 1163, 1087, 987, 813, 752, 673, 573,
553 cm−1. 1H NMR (CDCl3, 500 MHz): δ 7.90 (d, 2H, J = 8.0 Hz),
7.73 (d, 2H, J = 8.0 Hz), 7.60 (d, 2H, J = 8.0 Hz), 7.56 (d, 2H, J = 8.0
Hz), 4.79 (s, 2H), 2.11 (s, 3H). 13C{1H} NMR (CDCl3, 125 MHz): δ
197.7, 143.5, 136.0, 132.6, 132.3, 132.1, 131.9, 129.8, 129.3, 48.6,
22.9. HRMS (ESI): calcd for C15H14BrNO3S, [M+] 366.9877; found,
366.9881. Anal. Calcd for C15H14BrNO3S: C, 48.92; H, 3.83; N, 3.80.
Found: C, 49.22; H, 3.60; N, 3.59.
for C10H13NO3S: C, 52.85; H, 5.77; N, 6.16. Found: C, 53.17; H,
5.97; N, 5.94.
N-Tosylfuran-2-carboxamide (9b).33e Eluent in chromatography:
n-hexane/EtOAc 24:1. White solid, yield 79 mg, 60%. mp 126−127
°C. IR (KBr): (ν) 3266, 2960, 1702, 1560, 1412, 1338, 1165, 1120,
1
1011, 960, 863, 662 cm−1. H NMR (CDCl3, 500 MHz): δ 8.70 (s,
1H), 7.76 (d, 2H, J = 11.0 Hz), 7.65 (s, 1H), 7.26 (d, 2H, J = 10.5
Hz), 7.23 (d, 1H, J = 4.5 Hz), 6.55 (t, 1H, J = 2.5 Hz), 2.32 (s, 3H);
13C{1H} NMR (CDCl3, 125 MHz): δ 160.2, 154.2, 145.3, 145.2,
134.8, 130.2, 128.2, 118.9, 112.2, 21.7. HRMS (ESI): calcd for
C12H11NO4S, [M+] 265.0408; found, 265.0406. Anal. Calcd for
C12H11NO4S: C, 54.33; H, 4.18; N, 5.28. Found: C, 54.12; H, 4.47;
N, 4.97.
N-Tosylbenzamide (9c).33f Eluent in chromatography: n-hexane/
EtOAc 24:1. White solid, yield 79 mg, 58%. mp 124−125 °C. IR
(KBr): (ν) 3308, 1693, 1452, 1417, 1160, 1153, 838, 706, 653 cm−1.
1H NMR (CDCl3, 500 MHz): δ 8.97 (br s, 1H), 7.75 (d, 2H, J = 8.0
Hz), 7.39−7.46 (m, 5H), 7.28 (d, 2H, J = 8.0 Hz), 2.37 (s, 3H).
13C{1H} NMR (CDCl3, 125 MHz): δ 170.4, 144.8, 135.1, 133.9,
131.5, 130.0, 129.3, 128.6, 128.3, 21.8. HRMS (ESI): calcd for
C14H13NO3S, [M+] 275.0616; found, 275.0619. Anal. Calcd for
C14H13NO3S: C, 61.07; H, 4.76; N, 5.09. Found: C, 61.31; H, 5.03;
N, 5.40.
4-Methoxy-N-tosylbenzamide (9d).33f Eluent in chromatography:
n-hexane/EtOAc 19:1. White solid, yield 82 mg, 54%. mp 150−151
°C. IR (KBr): (ν) 3226, 1669, 1438, 1253, 1163, 1021, 836, 362
cm−1. 1H NMR (CDCl3, 500 MHz): δ 8.87 (s, 1H), 7.99 (d, 2H, J =
7.5 Hz), 7.74 (d, 2H, J = 7.5 Hz), 7.26 (d, 2H, J = 8.0 Hz), 6.94 (d,
2H, J = 8.0 Hz), 3.81 (s, 3H), 2.36 (s, 3H). 13C{1H} NMR (CDCl3,
125 MHz): δ 164.8, 144.4, 135.7, 132.2, 129.9, 128.0, 126.5, 125.3,
114.8, 55.8, 21.7. HRMS (ESI): calcd for C15H15NO4S, [M+]
305.0721; found, 305.0727. Anal. Calcd for C15H15NO4S: C, 59.00;
H, 4.95; N, 4.59. Found: C, 58.67; H, 4.74; N, 4.88.
N-(2-(3-Chlorophenyl)-2-oxoethyl)-4-methylbenzenesulfona-
mide (7d).33c Eluent in chromatography: n-hexane/EtOAc 24:1.
Colourless oil, yield 113 mg, 70%. IR (KBr): (ν) 3261, 2905, 1695,
1
1545, 1312, 1204, 1082, 756 cm−1. H NMR (CDCl3, 500 MHz): δ
4-Chloro-N-tosylbenzamide (9e).33f Eluent in chromatography: n-
hexane/EtOAc 24:1. White solid, yield 109 mg, 71%. mp 172−173
°C. IR (KBr): (ν) 3354, 1704, 1591, 1338, 1132, 1077, 811, 756, 663
cm−1. 1H NMR (CDCl3, 500 MHz): δ 7.97 (d, 2H, J = 8.5 Hz), 7.75
(d, 2H, J = 8.0 Hz), 7.39 (d, 2H, J = 8.0 Hz), 7.26 (d, 2H, J = 8.0 Hz),
4.82 (br s, 1H), 2.37 (s, 3H). 13C{1H} NMR (CDCl3, 125 MHz): δ
165.5, 142.8, 138.5, 138.2, 130.8, 128.9, 128.1, 126.8, 125.7, 21.9.
HRMS (ESI): calcd for C14H12ClNO3S, [M+] 309.0226; found,
309.0229. Anal. Calcd for C14H12ClNO3S: C, 54.28; H, 3.90; N, 4.52.
Found: C, 54.56; H, 3.70; N, 4.77.
8.02 (s, 1H), 7.93 (d, 1H, J = 8.0 Hz), 7.85 (br s, 1H), 7.73 (d, 2H, J
= 8.0 Hz), 7.55 (d, 1H, J = 8.0 Hz), 7.33−7.41 (m, 3H), 4.80 (s, 2H),
2.41 (s, 3H). 13C{1H} NMR (CDCl3, 125 MHz): δ 197.6, 139.6,
135.6, 135.1, 134.4, 132.5, 130.5, 129.7, 129.2, 128.0, 125.9, 50.8,
21.8. HRMS (ESI): calcd for C15H14ClNO3S, [M+] 323.0382; found,
323.0381. Anal. Calcd for C15H14ClNO3S: C, 55.64; H, 4.36; N, 4.33.
Found: C, 55.96; H, 4.64; N, 4.06.
N-(2-(3-Methoxyphenyl)-2-oxoethyl)-4-methylbenzenesulfona-
mide (7e).33c Eluent in chromatography: n-hexane/EtOAc 24:1.
Yellowish viscous oil, yield 84 mg, 53%. IR (KBr): (ν) 3260, 1695,
1320, 1255, 1150 cm−1. 1H NMR (CDCl3, 500 MHz): δ 7.96 (s, 1H,
−NH−), 7.78 (d, 2H, J = 7.5 Hz, Ts), 7.40 (s, 1H), 7.28−7.36 (m,
3H), 7.11 (d, 2H, J = 8.0 Hz), 4.80 (s, 2H), 3.81 (s, 3H), 2.39 (s,
3H). 13C{1H} NMR (CDCl3, 125 MHz): δ 198.5, 160.2, 139.7, 135.9,
134.8, 130.2, 129.5, 128.2, 120.9, 120.3, 118.0, 55.7, 50.7, 22.0.
HRMS (ESI): calcd for C16H17NO4S, [M+] 319.0878; found,
319.0877. Anal. Calcd for C16H17NO4S: C, 60.17; H, 5.37; N, 4.39.
Found: C, 60.40; H, 5.61; N, 4.66.
4-Nitro-N-tosylbenzamide (9f).34a Eluent in chromatography: n-
hexane/EtOAc 19:1. White solid, yield 126 mg, 79%. mp 199−200
°C. IR (KBr): (ν) 3231, 3067, 2922, 1676, 1608, 1534, 1446, 1343,
1163, 712 cm−1. 1H NMR (CDCl3, 500 MHz): δ 8.19 (d, 2H, J = 8.5
Hz), 8.11 (d, 2H, J = 8.5 Hz), 7.69 (d, 2H, J = 8.5 Hz), 7.47 (d, 2H, J
= 8.5 Hz), 4.42 (s, 1H), 2.11 (s, 3H). 13C{1H} NMR (CDCl3, 125
MHz): δ 163.9, 150.1, 144.2, 137.6, 136.8, 130.1, 128.4, 127.4, 124.6,
21.2. HRMS (ESI): calcd for C14H12N2O5S, [M+] 320.0466; found,
320.0467. Anal. Calcd for C14H12N2O5S: C, 52.49; H, 3.78; N, 8.75.
Found: C, 52.71; H, 3.57; N, 9.08.
N-(2-(2-Chlorophenyl)-2-oxoethyl)-4-methylbenzenesulfona-
mide (7f).33b Eluent in chromatography: n-hexane/EtOAc 24:1.
Colourless oil, yield 118 mg, 73%. IR (KBr): (ν) 3259, 2903, 1693,
4-Methyl-N-tosylbenzamide (9g).33f Eluent in chromatography: n-
hexane/EtOAc 24:1. White solid, yield 82 mg, 57%. mp 124−126 °C.
1
1544, 1313, 1201, 1079, 760 cm−1. H NMR (CDCl3, 500 MHz): δ
1
IR (KBr): (ν) 3294, 1694, 1394, 1153, 842, 656 cm−1. H NMR
7.67 (d, 2H, J = 7.5 Hz), 7.27−7.42 (m, 6H), 4.78 (s, 2H), 2.39 (s,
3H). 13C{1H} NMR (CDCl3, 125 MHz): δ 195.7, 143.7, 134.8, 134.4,
133.6, 132.5, 131.6, 131.4, 130.3, 128.8, 127.3, 52.7, 22.0. HRMS
(ESI): calcd for C15H14ClNO3S, [M+] 323.0382; found, 323.0381.
Anal. Calcd for C15H14ClNO3S: C, 55.64; H, 4.36; N, 4.33. Found: C,
55.83; H, 4.58; N, 4.08.
(CDCl3, 500 MHz): δ 9.86 (s, 1H), 7.92 (d, 2H, J = 8.0 Hz), 7.73 (d,
2H, J = 8.0 Hz), 7.24 (d, 2H, J = 8.0 Hz), 7.18 (d, 2H, J = 8.0 Hz),
2.34 (s, 3H), 2.30 (s, 3H). 13C{1H} NMR (CDCl3, 125 MHz): δ
170.2, 145.7, 144.5, 137.4, 130.3, 130.2, 129.9, 129.7, 129.2, 21.9,
21.7. HRMS (ESI): calcd for C15H15NO3S, [M+] 289.0772; found,
289.0778. Anal. Calcd for C15H15NO3S: C, 62.26; H, 5.23; N, 4.84.
Found: C, 61.93; H, 5.53; N, 4.53.
N-Tosylpropionamide (9a).33d Eluent in chromatography: n-
hexane/EtOAc 97:3. White solid, yield 43 mg, 38%. mp 110−112
°C. IR (KBr): (ν) 3428, 3080, 1639, 1435, 1336, 1264, 1155, 1088
cm−1. 1H NMR (CDCl3, 500 MHz): δ 9.35 (s, 1H), 7.76 (d, 2H, J =
8.0 Hz), 7.25 (d, 2H, J = 7.5 Hz), 2.38 (s, 3H), 2.33 (q, 2H, J = 15.0,
7.5 Hz), 1.09 (t, 3H, J = 7.5 Hz). 13C{1H} NMR (CDCl3, 125 MHz):
δ 172.4, 143.4, 137.5, 129.7, 126.4, 29.7, 21.5, 8.2. HRMS (ESI):
calcd for C10H13NO3S, [M+] 227.0616; found, 227.0614. Anal. Calcd
2-Chloro-N-tosylbenzamide (9h).33f Eluent in chromatography: n-
hexane/EtOAc 24:1. White solid, yield 120 mg, 78%. mp 114−116
°C. IR (KBr): (ν) 3249, 3062, 2854, 1702, 1593, 1441, 1342, 1172,
752 cm−1. 1H NMR (CDCl3, 500 MHz): δ 9.36 (s, 1H), 7.89 (d, 1H,
J = 7.5 Hz), 7.78 (d, 2H, J = 8.0 Hz), 7.32−7.40 (m, 3H), 7.23 (d,
2H, J = 8.0 Hz), 2.31 (s, 3H). 13C{1H} NMR (CDCl3, 125 MHz): δ
166.9, 145.0, 135.8, 133.7, 132.6, 131.6, 130.6, 130.3, 130.0, 128.4,
G
https://dx.doi.org/10.1021/acs.joc.0c02219
J. Org. Chem. XXXX, XXX, XXX−XXX

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Article
127.5, 21.8. HRMS (ESI): calcd for C14H12ClNO3S, [M+] 309.0226;
found, 309.0232. Anal. Calcd for C14H12ClNO3S: C, 54.28; H, 3.90;
N, 4.52. Found: C, 54.07; H, 3.61; N, 4.72.
ASSOCIATED CONTENT
* Supporting Information
■
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.joc.0c02219.
2-Hydroxy-N-tosylbenzamide (9i).34b Eluent in chromatography:
n-hexane/EtOAc 19:1. Colourless oily solid, yield 75 mg, 52%. IR
(KBr): (ν) 3340, 3307, 1692, 1453, 1418, 1163, 1150, 842, 703, 652
cm−1. 1H NMR (CDCl3, 500 MHz): δ 9.03 (s, 1H), 7.80 (d, 1H, J =
8.0 Hz), 7.75 (d, 2H, J = 7.5 Hz), 7.53−7.58 (m, 1H), 7.43−7.49 (m,
1H), 7.29 (d, 1H, J = 8.0 Hz), 7.25 (d, 2H, J = 8.0 Hz), 4.86 (s, 1H),
2.37 (s, 3H). 13C{1H} NMR (CDCl3, 125 MHz): δ 162.3, 145.3,
137.5, 135.6, 135.4, 134.0, 131.5, 130.2, 129.9, 128.1, 126.6, 21.7.
HRMS (ESI): calcd for C14H13NO4S, [M+] 291.0565; found,
291.0562. Anal. Calcd for C14H13NO4S: C, 57.72; H, 4.50; N, 4.81.
Found: C, 57.53; H, 4.42; N, 4.89.
1
Detailed copies of H and 13C NMR spectra (PDF)
AUTHOR INFORMATION
Corresponding Author
■
Ankita Rai − School of Physical Sciences, Jawaharlal Nehru
University, New Delhi 110 067, India; orcid.org/0000-
0002-2962-7427; Email: ankitarai@mail.jnu.ac.in
2-Nitro-N-tosylbenzamide (9j).34c Eluent in chromatography: n-
hexane/EtOAc 19:1. White solid, yield 134 mg, 84%. mp 122−123
°C. IR (KBr): (ν) 3213, 3070, 2850, 1706, 1593, 1448, 1352, 1170,
Authors
Prashant Shukla − School of Physical Sciences, Jawaharlal
Nehru University, New Delhi 110 067, India
1
740 cm−1. H NMR (CDCl3, 500 MHz): δ 10.37 (s, 1H), 8.06 (d,
Ambika Asati − Department of Chemistry, Guru Ghasidas
Vishwavidyalaya, Bilaspur, Chhattisgarh 495 009, India
Smita R. Bhardiya − Department of Chemistry, Guru Ghasidas
Vishwavidyalaya, Bilaspur, Chhattisgarh 495 009, India
Manorama Singh − Department of Chemistry, Guru Ghasidas
Vishwavidyalaya, Bilaspur, Chhattisgarh 495 009, India;
orcid.org/0000-0001-5872-6160
Vijai K. Rai − Department of Chemistry, Guru Ghasidas
Vishwavidyalaya, Bilaspur, Chhattisgarh 495 009, India;
orcid.org/0000-0002-6376-9576
1H, J = 7.5 Hz), 7.90 (d, 1H, J = 7.5 Hz), 7.81 (t, 1H, J = 8.0 Hz),
7.75 (d, 2H, J = 7.5 Hz), 7.63 (s, 1H), 7.25 (d, 2H, J = 7.5 Hz), 2.36
(s, 3H); 13C{1H} NMR (CDCl3, 125 MHz): δ 163.5, 143.8, 139.1,
134.3, 133.9, 132.8, 130.6, 129.9, 129.8, 126.6, 124.7, 21.7. HRMS
(ESI): calcd for C14H12N2O5S, [M+] 320.0466; found, 320.0458.
Anal. Calcd for C14H12N2O5S: C, 52.49; H, 3.78; N, 8.75. Found: C,
52.16; H, 3.57; N, 8.94.
3-Chloro-N-tosylbenzamide (9k).33f Eluent in chromatography: n-
hexane/EtOAc 24:1. White solid, yield 115 mg, 75%. mp 138−139
°C. IR (KBr): (ν) 3289, 1697, 1512, 1362, 1127, 915, 808, 742, 662
cm−1. 1H NMR (CDCl3, 500 MHz): δ 8.03 (s, 1H), 7.94 (d, 1H, J =
8.0 Hz), 7.75 (d, 2H, J = 8.0 Hz), 7.53 (d, 1H, J = 7.5 Hz), 7.37 (t,
1H, J = 7.5 Hz), 7.25 (d, 2H, J = 8.0 Hz), 5.05 (br s, 1H), 2.13 (s,
3H). 13C{1H} NMR (CDCl3, 125 MHz): δ 170.8, 139.5, 134.9, 134.0,
131.8, 130.4, 130.0, 129.9, 129.1, 128.5, 126.6, 21.7. HRMS (ESI):
calcd for C14H12ClNO3S, [M+]309.0226; found, 309.0222. Anal.
Calcd for C14H12ClNO3S: C, 54.28; H, 3.90; N, 4.52. Found: C,
54.06; H, 4.15; N, 4.78.
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.joc.0c02219
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
3-Nitro-N-tosylbenzamide (9l).34d Eluent in chromatography: n-
hexane/EtOAc 24:1. White solid, yield 129 mg, 81%. mp 170−172
°C. IR (KBr): (ν) 3251, 3084, 2873, 1701, 1614, 1532, 1442, 1344,
The SERB, DST, New Delhi, for INSPIRE Faculty Research
Award (IFA12-CH-61) and JNU for UPE-II (217) are
acknowledged for financial assistance and AIRF and JNU for
providing microanalyses and spectra. Authors also acknowl-
edge DST Purse-II support and DST-FIST-II, 2013 program
for sanctioning funds to purchase Flash chromatography. P.S.
thanks the UGC for Junior Research Fellowship (R. no. 23/
06/2013(i)EU-V).
1
1167, 865, 713 cm−1. H NMR (CDCl3, 500 MHz): δ 9.04 (s, 1H),
8.70 (s, 1H), 8.38 (d, 1H, J = 7.0 Hz), 8.19 (d, 1H, J = 7.5 Hz), 7.84
(d, 2H, J = 8.0 Hz), 7.65 (t, 1H, J = 8.0 Hz), 7.32 (d, 2H, J = 8.0 Hz),
2.39 (s, 3H). 13C{1H} NMR (CDCl3, 125 MHz): δ 167.6, 148.8,
145.5, 136.6, 134.2, 134.0, 130.6, 130.2, 129.8, 128.5, 125.5, 21.9.
HRMS (ESI): calcd for C14H12N2O5S, [M+] 320.0466; found,
320.0460. Anal. Calcd for C14H12N2O5S: C, 52.49; H, 3.78; N,
8.75. Found: C, 52.16; H, 3.51; N, 9.08.
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