Metal-Free Amidation Reactions of Terminal Alkynes with Benzenesulfonamide

Article abstract of DOI:10.1021/acs.joc.8b03065

A novel and efficient approach has been developed to synthesize α-sulfonylamino ketones through the reaction between terminal alkynes and sulfonamides under ambient air using PIDA (diacetoxy iodobenzene). A library of α-sulfonylamino ketone derivatives having a variety of substituents has been synthesized. A plausible reaction pathway has been predicted. This reaction offers a broad substrate scope, metal-free synthesis, excellent regioselectivity, easily accessible reactants, and room temperature reaction conditions under ambient air and is operationally simple. A gram-scale synthesis demonstrates the potential applications of the present method. In addition, we have also synthesized α-acetoxy ketones in the case of absence of sulfonamide.

Full text of DOI:10.1021/acs.joc.8b03065

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Article
Metal-Free Amidation Reactions of
Terminal Alkynes with Benzenesulfonamide
SACHINTA MAHATO, Sougata Santra, Grigory V Zyryanov, and Adinath Majee
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b03065 • Publication Date (Web): 26 Feb 2019
Downloaded from http://pubs.acs.org on February 26, 2019
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Metal-Free Amidation Reactions of Terminal Alkynes with
Benzenesulfonamide
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Sachinta Mahato,a Sougata Santra,b Grigory V. Zyryanovbc and Adinath Majeea*
a
Department of Chemistry; Visva-Bharati (A Central University), Santiniketan 731235, India.
E-mail: adinath.majee@visva-bharati.ac.in
b
Department of Organic and Biomolecular Chemistry, Chemical Engineering Institute, Ural
Federal University, 19 Mira Street, 620002, Yekaterinburg, Russian Federation.
I. Ya. Postovskiy Institute of Organic Synthesis, Ural Division of the Russian Academy of
Sciences, 22 S. Kovalevskoy Street, 620219 Yekaterinburg, Russian Federation.
c
PIDA
H
N
O
O
S
R
+
R1 SO2NH2
R1
CH3CN, rt
10 h
R
R = aryl/heteroaryl
R1 = aryl
O
C-N bond formation
Metal-free
21 examples
up to 87% yield
Aerobic conditions
Wide Substrates Scope
Room temperature
Abstract: A novel and efficient approach has been developed to synthesize α-sulfonylamino
ketones through the reaction between terminal alkynes and sulfonamides under ambient air using
PIDA (diacetoxy iodobenzene). A library of α-sulfonylamino ketone derivatives having a variety
of substituents has been synthesized. A plausible reaction pathway has been predicted. This
reaction offers a broad substrate scope, metal-free synthesis, excellent regioselectivity, easily
accessible reactants, room temperature reaction conditions under ambient air, and is
operationally simple. A gram-scale synthesis demonstrates the potential applications of the
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present method. In addition, we have also synthesized α-acetoxy ketones in case of absence of
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sulfonamide.
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Introduction:
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α-Amino ketones serve a significant role in organic chemistry as they are found in a large variety
of biologically active natural products. Commercial medicines such as mephedrone1 and
bupropion2 (Figure 1) contain α-amino ketones as well as the proteasome inhibitor epoxomicin.3
In organic synthesis, this moiety is also very useful for the preparation of 2-amino alcohols4 and
nitrogen-containing heterocycles (Figure 2).5
Figure 1: Commercial Medicines Containing α-Amino Ketones
O
H
N
O
H
N
Cl
CH3
CH3
CH3
C
CH3
CH3 CH3
H3C
Mephadrone
Bupropion
Figure 2: Nitrogen-Containing Heterocycles Synthesized from α-Amino Ketones
R2
R2
O
Ph
NC
NC
O
R
O
R
R
N
N
N
H2N
H2N
S
S
S
O
O
O
O
O
O
R1
R1
R1
ref 5(c)
ref 5(a)
ref 5(b)
Scheme 1: Different Strategies for the Synthesis of α-Sulfonylamino Ketones
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Previous Works
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Catalyst, DMSO, heat
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8
(ref 6)
O
H
N
NBS/CAN, solvent, heat
(ref 7)
R3
N
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R1
R3
R2
IBX/ -CD,H2O
(ref 8)
R1
R2
R1 = aromatic,aliphatic
R2 = H, Me, Et
R3 = COC6H5NO2, COOEt
pyridine N-oxide
(ref 9)
solvent, heat,
SO2Ph, Ts
O
OTMS
catalyst or PIDA, PhI=NTs
NHTs
R1
R1
(ref 10)
R2
solvent
R2
N
O
H
cat Rh(II)
NSO2R2
N
N SO2R2
R1
(ref 11)
H2O
R1
R1 = aromatic, aliphatic
R2 = Ts, Ms
O
H
R3O2S
N
O
R2
base, solvent
R2CN
NSO2R3
N
R1
R1
(ref 12)
R1= ayl, alkyl
R2= Ts, Ms, SO2Ph
Our Work
R1
O
PIDA (0.25 equiv)
CH3CN, rt, 10 h
O
H
N
R1
S NH2
O
O
S
R
+
R
1
O
2
R = aryl, heteroaryl
R1 = H, Me, Cl
3
Owing to their importance, synthetic organic chemists have attempted various
methodologies based on different modifications (Scheme 1). Some of the methodologies are the
oxidative ring opening of aziridines by DMSO,6 NBS combined with CAN,7 IBX in the presence
of β-cyclodextrin,8 or pyridine N-oxide.9 Another way to synthesize α-amino ketones is through
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umpolung process using silyl enol ethers, followed by nucleophilic addition of amines.10
Additionally, a rhodium-catalyzed denitrogenative hydration of N-sulfonyl-1,2,3-triazoles was
reported by Murakami et al.11 Recently, Zhan et al.12 prepared sulfonylamino ketones via
Cs2CO3 promoted N-N bond cleavage from hydrazones precursor. As oxidants, hypervalent
iodine reagents have recently received much attention due to their low toxicity, mild reactivity,
ready availability, high stability, and easy handling.13 They are useful oxidants in various
coupling reactions.14 Our group is actively engaged in developing various methodologies15 in
organic synthesis involving the chemistry of C-N bond forming/cleavage reactions.16 Herein, we
report a fully different approach from the reported methods using (diacetoxy)iodobenzene
(phenyliodine(III) diacetate, (PIDA)14b to synthesize α-amino ketones under ambient
temperature. We have observed that the reaction of terminal alkynes with benzenesulfonamide
affords α-amino ketones (α-sulfonylamino ketones) in good to excellent yields in presence of
PIDA as oxidant (Scheme 1).
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Results and Discussion:
We started our study by mixing phenylacetylene (1a, 0.5 mmol) and 4-
methylbenzenesulfonamide (2a, 0.5 mmol) using PIDA (1 equiv) as oxidant, at room
temperature in acetonitrile solvent. Gratifyingly, benzenesulfonamide (the α-sulfonylamino
ketone, 3a) was obtained in 65% yield along with 12% of α-acetoxyacetophenone (4a) after 10 h
(Table 1, entry 1). Encouraged by this result, we carried out the reaction in different conditions
to optimize the reaction, and the results are summarized in Table 1. At first, we investigated the
loading effect of the oxidant (PIDA) and sulfonamide (TsNH2, 2a) in different ratios. Using 0.5
equiv of PIDA and 1 equiv of TsNH2 (2a), the yields of 3a and 4a were 74% and <5%
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respectively (Table 1, entry 2). When the amount of PIDA was decreased to 0.25 equiv. the
desired product (3a) was obtained in 80% yield along with trace amount of 4a (Table 1, entry 3).
Again, with increasing the amount of TsNH2 (2a) from 1 to 2 equiv. no enhancement of the yield
was noticed (Table 1, entry 4). The yield of the reaction did not improve significantly by
increasing the reaction time, but upon reducing the reaction time, the yield of 3a was lowered
considerably (Table 1, entries 6 ). Based on these observations we concluded that using 0.25
equiv. of PIDA and 1 equiv. of the TsNH2 (2a) in acetonitrile solvent gave the best result after 10
h (Table 1, entry 3).
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Table 1: Optimization of the PIDA Driven Amidationa
O
O
PIDA
H
Ph
TsNH2
OAc
+
+
N
Ph
Ph
Ts
CH3CN, rt
2a
1a
4a
3a
Entry PIDA (equiv) TsNH2 (equiv) time (h) conversion (%) yield of
yield of
4a (%)b
12
3a (%)b
1
2
3
4
5
6
1
1
1
1
2
1
1
10
10
10
10
20
6
77
78
82
83
84
48
65
74
80
81
81
45
0.5
<5
0.25
0.25
0.25
0.25
trace
trace
trace
trace
aReaction conditions: All reaction are carried out in 0.5 mmol scales, 1a (0.5 mmol), 2a (as
stated amount) and oxidant (PIDA), at room temperature in MeCN. b Isolated yield.
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Next, a series of experiments have been carried out to examine the role of solvents which
are summarized in Table 2. Considering the green concept, we have tried the reaction in water
(Table 2, entry 1) and isolated only 4a in a 36% yield with a trace amount of 3a. Whereas in
methanol, the desired product (3a) was obtained in 25% yield along with 20% of 4a (Table 2,
entry 2). Next, nonpolar aprotic solvent like toluene showed moderate conversion (52%) with
22% of 3a and 30% of 4a (Table 2, entry 3), but surprisingly in other aprotic polar solvents like
1,2-DCE and 1,4-dioxane, 3a was obtained in lower amounts, but the yields were 30-32% for 4a
(Table 2, entries 4 & 5). In the case of acetonitrile, we got the best result (80% yield of 3a) and
trace amount of product 4a with 82% conversion (Table 2, entry 6). Thus, the optimized reaction
condition was achieved using 0.25 equiv of PIDA and 1 equiv of the TsNH2 (2a) with respect to
phenylacetylene (1a) at room temperature in MeCN for 10 h (Table 2, entry 6).
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Table 2: Screening of the Solvent Effects of the Amidation Reactionsa
O
O
PIDA (0.25 equiv)
H
Ph
+ TsNH2
N
OAc
+
Ph
Ts
Ph
Solvent (2 mL)
rt, 10 h
2a
1a
1 equiv
4a
3a
1 equiv
entry solvent
conversion (%)
yield of 3a (%)b yield of 4a (%)b
1
2
3
4
5
6
H2O
39
45
52
42
33
82
Trace
25
36
MeOH
20
Toluene
1,2-DCE
1,4-Dioxane
CH3CN
22
30
10
32
Trace
80
30
Trace
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a Reaction conditions: All reaction are carried out in 0.5 mmol scale; 1a (0.5 mmol), 2a (1 equiv)
5
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b
and oxidant (PIDA, 0.25 equiv), at room temperature in different solvents (2 mL) for 10 h.
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Isolated yield.
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After optimizing the reaction conditions, we explored the substrate scope employing
different terminal alkynes to react with 4-methylbenzenesulfonamide, and the results are
summarized in Scheme 2. Phenylacetylene afforded the desired product (3a) in good yield. The
regioselectivity is very important for this reaction, and we found no effect on regioselectivity of
the reaction when phenylacetylene was used substituted with electron-donating or electron
withdrawing groups in the phenyl moiety. The presence of various electron-donating substituents
such as methyl (3b, 3c) and tert-butyl (3d) produced the desired products in good to excellent
yields (78-85%). Similarly, a variety of electron withdrawing groups like ketones, halogens (F,
Cl, Br) and nitro at different positions of the phenylacetylene substrate (3e-3k) also reacted
efficiently with good to excellent yields. The heterocyclic moiety, thiophene, afforded the
corresponding product with excellent yield (3l). It is worthy to mention that an aliphatic alkyne
also gave the desired product (3m) in excellent yield.
Scheme 2: Substrates Scope of the Amidation Reactiona
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R1
O
O
H
N
PIDA (0.25 equiv)
CH3CN, rt, 10 h
O
R1
S NH2
O
R
+
R
S
O
1
2
3
1
2a
2b
2c
R = Me ( ), Cl ( ), H (
)
9
O
H
N
O
H
N
O
H
N
O
H
N
O
H
N
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Ts
Ts
Ts
Ph
Ts
O
Ts
tBu
3d,
85%
3a,
80%
3e,
87%
3c,
84%
O
3b,
78%
H
O
H
N
O
H
N
O
H
N
N
Ts
Ts
Ts
Ts
F
Cl
Cl
3g,
82%
O
3h,
77%
3f,
84%
F
3i,
72%
H
N
O
H
N
O
H
O
H
N
N
Ts
Ts
Ts
Ts
S
Br
3l,
86%
3m,
87%
3j,
78%
3k,
81%
NO2
Cl
Cl
Cl
Cl
O
H
O
H
N
O
H
O
H
N
O
S
O
S
O
S
O
S
N
N
Ph
O
O
O
O
tBu
EtO
3p,
85%
3n,
83%
3o,
82%
3q,
78%
Cl
Cl
Cl
O
H
N
O
H
O
H
N
O
S
O
O
S
N
S
O
O
O
S
F
Br
O
3r,
84%
3t,
85%
3s,
82%
H
N
O
H
O
S
O
N
S
O
77%
O
83%
tBu
3v,
3u,
Unreactive substrates:
OH
N
H2N
1w
1y
1x
aReaction conditions: All reaction are carried out in 0.5 mmol scale, 1 (0.5 mmol), 2 (0.5 mmol)
and PIDA (0.25 equiv), at room temperature in MeCN (2 mL) for 10 h. All are isolated yields.
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Next, we have explored our present methodology with another sulfonamide to react with
terminal alkynes under the same reaction condition. 4-Chlorobenzenesulfonamide (2b) reacted
with different terminal alkynes. Phenylacetylene, substituted phenylacetylene with electron
donating substituents like –CH3, -C(CH3)3, -OEt, furnished the desired products with good to
excellent yields (3n-3q).Additionally, phenylacetylene substituted with electron-withdrawing
groups like –F, -Br afforded the desired products in good yields (3r & 3s). The thiophene-
containing substrate was found to be equally effective to afford the desired product (3t) with
good yield. Simple benzenesulfonamide (2c) also successfully reacted with phenylacetylene and
4-tert-butyl phenylacetylene to produce the desired products (3u & 3v) in good yields. However,
the present methodology is not applicable for the propargyl alcohol (1w), 4-ethynylaniline (1x)
and 2-ethynylpyridine (1y). All these reactions were carried out in an open atmosphere and are
not sensitive to air and moisture. The reaction conditions are mild and give no decomposition of
the products or polymerization of the starting materials. All of the known synthesized
compounds have been characterized by NMR and the new compounds by NMR and mass
spectrometry, and the X-ray crystallographic analysis of 4-methyl-N-(2-oxo-2-(thiophen-3-
yl)ethyl)benzenesulfonamide (3l) was performed to confirm the structure of the product as
shown in Figure 3.17
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Figure 3: Crystal Structure (ORTEP) of 4-Methyl-N-(2-oxo-2-(thiophen-3-
yl)ethyl)benzenesulfonamide (3l)
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Furthermore, the potential synthetic applicability of this method was investigated on the
gram scale using the model reaction in our laboratory setup. As shown in Scheme 3, the reaction
could afford 1.08 g of 3a in 75% yield without any significant loss of its efficiency,
demonstrating the potential applications of the present method for a large scale synthesis of α-
sulfonylamino ketone derivatives.
Scheme 3: Gram-Scale Synthesis
NH2
O S O
O
H
N
O
S
PIDA (0.25 equiv)
CH3CN, 10 h, rt
+
O
3a,
(
75%, 1.08 g)
2a,
(
5 mmol)
1a,
(
5 mmol)
Finally, we checked the reaction in absence of sulfonamide, and we isolated exclusively
84% of α-acetoxy ketone (4a) when the reaction was performed between phenylacetylene and 1
equiv of PIDA at room temperature.18 Different α-acetoxy ketone derivatives have been
synthesized by varying different phenylacetylenes (Scheme 4). Phenylacetylenes containing
electron-donating substituents such as methyl and tert-butyl afforded the products in 81% and
86% yields respectively (4b and 4c). Electron-withdrawing groups like -fluoro and -bromo
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formed α-acetoxy ketone derivatives in good to excellent yields (4d and 4e). Heterocyclic moiety
like 3-ethynylthiophene reacted well to afford corresponding product 4f in 84% yield.
7
8
9
Scheme 4: Substrates Scope of the α-Acetoxy Ketonesa
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O
PIDA (1 equiv)
R
OAc
R
CH3CN, rt
10 h
1
4
O
O
O
OAc
OAc
OAc
tBu
4c
, 86%
4a,
84%
4b
, 81%
O
O
O
OAc
F
OAc
Br
OAc
S
4f
, 84%
4d
4e
, 73%
, 80%
aReaction conditions: All reactions are carried out in 0.5 mmol scales, 1 (0.5 mmol) and
PIDA (1 equiv), at room temperature in MeCN (2 mL) for 10 h. All are isolated yields.
Based on the literature18a,c and our observation in absence of sulfonamide we propose the
reaction pathway shown in Scheme 5. Reaction of alkyne 1 with PhI(OAc)2 forms the
phenylalkynyl iodanyl acetate intermediate A which on Michael-type addition of AcOH provides
intermediate B. On removal of acetate the intermediate carbene C is formed which would then
react with an acetoxy nucleophile or acidic acid leading to a diacetoxy alkene intermediate D.
This one would then evolve to an α-acetoxy ketone 4 by reacting with the residual water, which
could then lead to the α–sulfonylamino ketone 3 when sulphonamides are present. When α-
acetoxy ketone 4a was subjected to react with sulphonamide 2a, it afforded the desired product
3a which supports our mechanistic path.
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Scheme 5: Proposed Mechanism
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H
AcOH
PhI(OAc)2
AcO
AcO
R
AcO
R
H
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OAc
-OAc
-PhI
:
C
R
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Ph
R
R
I
Ph
OAc
OAc
1
A
OAc
AcOH
D
B
C
H2O
OAc
R1SO2NH2
AcOH
O
H
N
O
R
SO2R1
R
3
4
Conclusion:
To conclude, we have successfully developed an efficient and regioselective methodology for the
synthesis of α-sulfonylamino ketones derivatives by the coupling of terminal alkynes with
sulfonamides in presence of PIDA at room temperature under ambient air. An array of α-
sulfonylamino ketones with broad functionalities have been synthesized in high yields. In
addition, we have also observed the formation of α-acetoxy ketones in absence of sulfonamide.
We have also proposed a mechanistic pathway for the formation of both of these compounds.
The notable advantages of the present methodology are clean reaction, easily accessible
reactants, ease of product isolation/purification, and metal-free and environmentally friendly
reaction conditions. We believe that the present methodology opens a new door to synthesize
important building blocks of α-sulfonylamino ketones.
Experimental Section:
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1
General information: H NMR spectra were determined on a 400 MHz spectrometer as
solutions in CDCl3. Chemical shifts are expressed in parts per million (δ) and the signals were
reported as s (singlet), d (doublet), t (triplet), m (multiplet) and coupling constants J were given
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in Hz. C NMR spectra were recorded at 100 MHz in CDCl3 solution. Chemical shifts are
expressed in parts per million (δ) and are referenced to CDCl3 (δ = 77.16) as an internal standard.
TLC was done on silica gel coated glass slide (Silica gel G for TLC). Silica gel (60-120 mesh)
was used for column chromatography. Petroleum ether refers to the fraction boiling in the range
of 60-80 °C unless otherwise mentioned. All solvents were dried and distilled before use.
Commercially available substrates were freshly distilled before the reaction. All reactions
involving moisture sensitive reactants were executed using oven dried glassware. All the starting
materials (such as terminal alkynes 1 and benzenesulfonamide 2) and other reagents were
purchased from commercial suppliers.
General procedure for the synthesis of α-amino ketones (3): A mixture of terminal alkyne (1,
0.5 mmol) and benzenesulfonamide (2, 0.5 mmol) was taken in 2 mL of CH3CN in a sealed tube.
Iodobenzene diacetate (PIDA, 0.25 equiv) was added to the reaction mixture. Next, the reaction
mixture was stirred at room temperature for 10 h. After completion of the reaction (monitored by
TLC), the reaction mixture was diluted with ethylacetate (10 mL) and water (10 mL). Then
organic layer was dried over anhydrous Na2SO4. After evaporation of solvent the crude product
was collected and purified by column chromatography on silica gel using petroleum ether/ethyl
acetate (8% to 10%) as eluent.
Typical
procedure
for
the
synthesis
of
4-methyl-N-(2-oxo-2-
phenylethyl)benzenesulfonamide (3a) on gram scale: A mixture of phenylacetylene (1a, 5
mmol) and 4-methylbenzenesulfonamide (2a, 5 mmol) was taken in 10 mL of CH3CN in a 25
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mL of round bottom flask. Iodobenzene diacetate (PIDA, 0.25 equiv) was added to the reaction
mixture. Next, the reaction mixture was stirred at room temperature for 10 h. After completion of
the reaction (monitored by TLC), the reaction mixture was diluted with ethylacetate (25 mL) and
water (25 ml). Then organic layer was dried over anhydrous Na2SO4. After evaporation of
solvent the crude product was purified by column chromatography on silica gel using petroleum
ether/ethyl acetate (8% to 10%) as eluent to get the analytically pure product as white solid (3a,
1.08 g, 75%).
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General procedure for the synthesis of α-acetoxy ketone (4): A mixture of terminal alkyne (1,
0.5 mmol) and iodobenzene diacetate (PIDA, 0.5 equiv) was taken in 2mL of CH3CN in a sealed
tube. Next, the reaction mixture was stirred at room temperature for 10 h. After completion of
the reaction (monitored by TLC), the reaction mixture was diluted with ethylacetate (10 mL) and
water (10 mL). Then organic layer was dried over anhydrous Na2SO4. After evaporation of
solvent the crude product was collected and purified by column chromatography on silica gel
using petroleum ether/ethyl acetate (5% to 6%) as eluent.
4-Methyl-N-(2-oxo-2-phenylethyl)benzenesulfonamide (3a):10c White solid (115 mg, 80%), mp:
116-118 °C; 1H NMR (CDCl3, 400 MHz): δ 7.86-7.83 (m, 2H), 7.79-7.77 (m, 2H), 7.62-7.59 (m,
1H), 7.48-7.44 (m, 2H), 7.29-7.27 (m, 2H), 5.65 (t, J = 8.0 Hz, 1H), 4.46 (d, J = 4.4 Hz, 2H),
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2.39 (s, 3H); C{1H} NMR (CDCl3, 100 MHz): δ 192.7, 143.9, 136.3, 134.5, 134.0, 130.0,
129.1, 128.0, 127.3, 48.8, 21.6.
4-Methyl-N-(2-oxo-2-(p-tolyl)ethyl)benzenesulfonamide (3b):11,10f White solid (118 mg, 78%),
mp: 120-121 °C; 1H NMR (CDCl3, 400 MHz): δ 7.71-7.66 (m, 4H), 7.22-7.18 (m, 4H), 5.59 (t, J
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= 8.4 Hz, 1H), 4.35 (d, J = 4.8 Hz, 2H), 2.34 (s, 3H), 2.32 (s, 3H); 13C{1H} NMR (CDCl3, 100
MHz): δ 192.1, 145.7, 143.9, 136.2, 131.4, 129.9, 129.8, 128.1, 127.3, 48.6, 21.9, 21.6.
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4-Methyl-N-(2-oxo-2-(m-tolyl)ethyl)benzenesulfonamide (3c):10f White solid (127 mg, 84%),
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mp: 127-128 °C ; H NMR (CDCl3, 400 MHz): δ 7.79-7.76 (m, 2H), 7.65-7.62 (m, 2H), 7.43-
7.40 (m, 1H), 7.36-7.28 (m, 3H), 5.66 (t, J = 8.4 Hz, 1H), 4.44 (d, J = 4.4 Hz, 2H), 2.39 (s, 6H);
13C{1H} NMR (CDCl3, 100 MHz): δ 192.8, 143.9, 139.1, 136.2, 135.4, 133.9, 130.0, 129.0,
128.5, 127.3, 125.2, 48.8, 21.6, 21.4.
N-(2-(4-(Tert-butyl)phenyl)-2-oxoethyl)-4-methylbenzenesulfonamide (3d):6g White solid (146
1
mg, 85%), mp: 117-119 °C; H NMR (CDCl3, 400 MHz): δ 7.79-7.76 (m, 4H), 7.48-7.46 (m,
2H), 7.29-7.27 (m, 2H), 5.68 (t, J = 8.8 Hz, 1H), 4.43 (d, J = 4.4 Hz, 2H), 2.39 (s, 3H), 1.32 (s,
9H); 13C{1H} NMR (CDCl3, 100 MHz): δ 192.2, 158.6, 143.8, 136.2, 131.3, 129.9, 128.0, 127.3,
126.1, 48.7, 35.4, 31.1, 21.6.
N-(2-(4-Acetylphenyl)-2-oxoethyl)-4-methylbenzenesulfonamide (3e):7a White solid (143 mg,
1
87%), mp: 116-118 °C; H NMR (CDCl3, 400 MHz): δ 8.03-8.01 (m, 2H), 7.94-7.92 (m, 2H),
7.79-7.77 (m, 2H), 7.31-7.28 (m, 2H), 5.63 (t, J = 8.4 Hz, 1H), 4.49 (d, J = 4.4 Hz, 2H), 2.63 (s,
3H), 2.40 (s, 3H); 13C{1H} NMR (CDCl3, 100 MHz): δ 197.2, 192.4, 144.0, 141.3, 137.0, 136.2,
130.0, 128.9, 128.3, 127.3, 49.2, 27.0, 21.7.
N-(2-(4-Fluorophenyl)-2-oxoethyl)-4-methylbenzenesulfonamide (3f): Colourless oil (128 mg,
84%); 1H NMR (CDCl3, 400 MHz): δ 7.90-7.87 (m, 2H), 7.78-7.76 (m, 2H), 7.29-7.27 (m, 2H),
7.15-7.11 (m, 2H), 5.66 (t, J = 8.4 Hz, 1H), 4.43 (d, J = 4.4 Hz, 2H), 2.39 (s, 3H); 13C{1H} NMR
1
3
(CDCl3, 100 MHz): δ 191.2, 166.5 (d, JC-F = 256 Hz), 143.9, 136.2, 130.8 (d, JC-F = 10 Hz),
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130.4 (d, JC-F = 3 Hz), 129.9, 127.3, 116.4 (d, JC-F = 23 Hz), 48.7, 21.6. Anal. Calcd. For
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6
C15H14FNO3S: C, 58.62; H, 4.59; N, 4.56%; Found: C, 58.68; H, 4.52; N, 4.67%.
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N-(2-(3-Fluorophenyl)-2-oxoethyl)-4-methylbenzenesulfonamide (3g): White solid (125 mg,
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82%), mp: 157-158 °C; H NMR (CDCl3, 400 MHz): δ 7.78-7.76 (m, 2H), 7.63-7.61 (m, 1H),
7.55-7.52 (m, 1H), 7.48-7.43 (m, 1H), 7.33-7.28 (m, 3H), 5.63 (t, J = 8.4 Hz, 1H), 4.44 (d, J =
4.4 Hz, 2H), 2.39 (s, 3H); 13C{1H} NMR (CDCl3, 100 MHz): δ 191.7, 163.0 (d, 1JC-F = 248 Hz),
3
3
4
144.0, 136.1, 135.8 (d, JC-F = 7 Hz), 130.9 (d, JC-F = 8 Hz), 130.0, 127.3, 123.7 (d, JC-F = 3
2
2
Hz), 121.6 (d, JC-F = 21 Hz), 114.8 (d, JC-F = 23 Hz), 49.0, 21.6. Anal. Calcd. For
C15H14FNO3S: C, 58.62; H, 4.59; N, 4.56%; Found: C, 58.52; H, 4.51; N, 4.48%.
N-(2-(4-Chlorophenyl)-2-oxoethyl)-4-methylbenzenesulfonamide (3h):10e White solid (131 mg,
1
77%), mp: 166-167 °C; H NMR (CDCl3, 400 MHz): δ 7.80-7.76 (m, 4H), 7.45-7.42 (m, 2H),
7.30-7.28 (m, 2H), 5.63 (t, J = 8.0 Hz, 1H), 4.42 (d, J = 4.8 Hz, 2H), 2.39 (s, 3H); 13C{1H} NMR
(CDCl3, 100 MHz): δ 191.6, 144.0, 141.1, 136.2, 132.2, 130.0, 129.5, 129.4, 127.3, 48.8, 21.6.
N-(2-(2-Chlorophenyl)-2-oxoethyl)-4-methylbenzenesulfonamide (3i):10e Colourless oil (122
1
mg, 72%); H NMR (CDCl3, 400 MHz): δ 7.77-7.75 (m, 2H), 7.48-7.40 (m, 3H), 7.34-7.28 (m,
3H), 5.56 (t, J = 8.4 Hz, 1H), 4.43 (d, J = 4.0 Hz, 2H), 2.41 (s, 3H); 13C{1H} NMR (CDCl3, 100
MHz): δ 192.1, 145.7, 143.7, 136.2, 131.4, 129.9, 129.8, 128.1, 127.3, 48.6, 21.9, 21.6.
N-(2-(4-Bromophenyl)-2-oxoethyl)-4-methylbenzenesulfonamide (3j):10e White solid (150 mg,
1
78%), mp: 120-122 °C; H NMR (CDCl3, 400 MHz): δ 7.78-7.76 (m, 2H), 7.72-7.69 (m, 2H),
7.63-7.59 (m, 2H), 7.30-7.28 (m, 2H), 5.60 (t, J = 8.4 Hz, 1H), 4.42 (d, J = 4.8 Hz, 2H), 2.40 (s,
3H); 13C{1H} NMR (CDCl3, 100 MHz): δ 191.8, 144.0, 136.2, 132.6, 132.5, 130.0, 129.9, 129.4,
127.3, 48.7, 21.7.
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4-Methyl-N-(2-(3-nitrophenyl)-2-oxoethyl)benzenesulfonamide (3k): Yellow solid (135 mg,
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6
1
81%), mp: 107-108 °C ; H NMR (CDCl3, 400 MHz): δ 8.66-8.65 (m, 1H), 8.47-8.44 (m, 1H),
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8
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8.20-8.18 (m, 1H), 7.79 (d, J = 8.4 Hz, 2H), 7.71 (t, J = 8 Hz, 1H), 7.30 (d, J = 8 Hz, 2H), 5.66
(t, J = 4.4 Hz, 1H), 4.53 (d, J = 4.8 Hz, 2H), 2.40 (s, 3H); 13C{1H} NMR (CDCl3, 100 MHz): δ
191.2, 148.6, 144.2, 136.1, 135.1, 133.5, 130.5, 130.0, 128.6, 127.3, 122.9, 49.2, 21.7. Anal.
Calcd. For C15H14N2O5S: C, 53.89; H, 4.22; N, 8.38%; Found: C, 53.81; H, 4.31; N, 8.46%.4-
Methyl-N-(2-oxo-2-(thiophen-3-yl)ethyl)benzenesulfonamide (3l):11 White solid (126 mg,
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86%), mp: 130-131 °C; H NMR (CDCl3, 400 MHz): δ 8.07-8.06 (m, 1H), 7.78-7.76 (m, 2H),
7.47-7.45 (m, 1H), 7.35-7.33 (m, 1H), 7.29-7.27 (m, 1H), 5.60 (t, J = 8.4 Hz, 1H), 4.34 (d, J =
4.8 Hz, 2H), 2.39 (s, 3H); 13C{1H} NMR (CDCl3, 100 MHz): δ 186.9, 143.9, 138.6, 136.1, 133.1,
129.9, 127.3(2C), 126.4, 49.3, 21.6.
4-Methyl-N-(2-oxo-4-phenylbutyl)benzenesulfonamide (3m): White solid (137 mg, 87%), mp:
1
92-93 °C; H NMR (CDCl3, 400 MHz): δ 7.64-7.62 (m, 2H), 7.22-7.15 (m, 4H), 7.12-7.09 (m,
1H), 7.02-7.00 (m, 2H), 5.27 (t, J = 9.2 Hz, 1H), 3.70 (d, J = 4.8 Hz, 2H), 2.76 (t, J = 14.8 Hz,
2H), 2.59 (t, J = 15.2 Hz, 2H), 2.34 (s, 3H); 13C{1H} NMR (CDCl3, 100 MHz): δ 203.1, 143.9,
140.0, 136.2, 129.9, 128.7, 128.3, 127.3, 126.5, 51.7, 41.7, 29.5, 217. Anal. Calcd. For
C17H19NO3S: C, 64.33; H, 6.03; N, 4.41%; Found: C, 64.42; H, 6.11; N, 4.48%.
4-Chloro-N-(2-oxo-2-phenylethyl)benzenesulfonamide (3n):6g White solid (128 mg, 83%), mp:
137-138 °C; 1H NMR (CDCl3, 400 MHz): δ 7.86-7.82 (m, 4H), 7.64-7.60 (m, 1H), 7.49-7.45 (m,
4H ), 5.73 (t, J = 8.4 Hz, 1H), 4.48 (d, J = 4.4 Hz, 2H); 13C{1H} NMR (CDCl3, 100 MHz): δ
192.4, 139.6, 137.9, 134.7, 133.8, 129.6, 129.2, 128.7, 128.0, 48.7.
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4-Chloro-N-(2-oxo-2-(p-tolyl)ethyl)benzenesulfonamide (3o): Colourless oil (132 mg, 82%);
1H NMR (CDCl3, 400 MHz): δ 7.78-7.74 (m, 2H), 7.68-7.66 (m, 2H), 7.41-7.37 (m, 2H), 7.21-
7.18 (m, 2H), 5.68 (t, J = 8.8 Hz, 1H), 4.37 (d, J = 4.4 Hz, 2H), 2.34 (s, 3H); 13C{1H} NMR
(CDCl3, 100 MHz): δ 192.0, 145.9, 139.5, 137.9, 131.3, 129.8, 129.6, 128.7, 128.1, 48.6, 21.9.
Anal. Calcd. For C15H14ClNO3S: C, 55.64; H, 4.36; N, 4.33%; Found: C, 55.55; H, 4.28; N,
4.27%.
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N-(2-(4-(Tert-butyl)phenyl)-2-oxoethyl)-4-chlorobenzenesulfonamide (3p): White solid (155
1
mg, 85%), mp: 145-146 °C; H NMR (CDCl3, 400 MHz): δ 7.84-7.77 (m, 4H), 7.49-7.44 (m,
4H), 5.77 (t, J = 8.8 Hz, 1H), 4.45 (d, J = 4.8 Hz, 2H), 1.32 (s, 9H); 13C{1H} NMR (CDCl3, 100
MHz): δ 192.0, 158.8, 139.5, 137.9, 131.2, 129.6, 128.7, 128.0, 126.1, 48.6, 35.4, 31.1. Anal.
Calcd. For C18H20ClNO3S: C, 59.09; H, 5.51; N, 3.83%; Found: C, 59.19; H, 5.60; N, 3.92%.
4-Chloro-N-(2-(4-ethoxyphenyl)-2-oxoethyl)benzenesulfonamide (3q): White solid (137 mg,
1
78%), mp: 153-154 °C; H NMR (CDCl3, 400 MHz): δ 7.84-7.80 (m, 4H), 7.47-7.45 (m, 2H),
6.93-6.90 (m, 2H), 5.74 (t, J = 8.4 Hz, 1H), 4.40 (d, J = 4.4 Hz, 2H), 4.12-4.07 (m, 2H), 1.44 (t, J
= 13.6 Hz, 3H); 13C{1H} NMR (CDCl3, 100 MHz): δ 190.6, 164.2, 139.5, 137.9, 130.4, 129.6,
128.7, 126.5, 114.8, 64.1, 48.3, 14.7. Anal. Calcd. For C16H16ClNO4S: C, 54.32; H, 4.56; N,
3.96%; Found: C, 54.41; H, 4.65; N, 3.88%.
4-Chloro-N-(2-(4-fluorophenyl)-2-oxoethyl)benzenesulfonamide (3r): White solid (137 mg,
1
84%), mp: 124-126 °C; H NMR (CDCl3, 400 MHz): δ 7.91-7.87 (m, 2H), 7.84-7.82 (m, 2H),
7.48-7.46 (m, 2H), 7.17-7.13 (m, 2H), 5.74 (t, J = 8.4 Hz, 1H), 4.45 (d, J = 4.4 Hz, 2H); 13C{1H}
1
3
NMR (CDCl3, 100 MHz): δ 190.9, 166.7 (d, JC-F = 256 Hz), 139.6, 137.9, 130.8 (d, JC-F = 9
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Hz), 130.2 (d, JC-F = 2 Hz), 129.7, 128.7, 116.5 (d, JC-F = 22 Hz), 48.6. Anal. Calcd. For
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C14H11ClFNO3S: C, 51.30; H, 3.38; N, 4.27%; Found: C, 51.23; H, 3.30; N, 4.18%.
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N-(2-(4-Bromophenyl)-2-oxoethyl)-4-chlorobenzenesulfonamide (3s): White solid (159 mg,
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82%), mp: 138-139 °C; H NMR (CDCl3, 400 MHz): δ 7.84-7.82 (m, 2H), 7.72-7.70 (m, 2H),
7.63-7.61 (m, 2H), 7.48-7.45 (m, 2H), 5.71 (t, J = 8.4 Hz, 1H), 4.44 (d, J = 4.4 Hz, 2H); 13C{1H}
NMR (CDCl3, 100 MHz): δ 191.6, 139.7, 137.9, 132.6, 132.5, 130.1, 129.7, 129.4, 128.7, 48.7.
Anal. Calcd. For C14H11BrClNO3S: C, 43.27; H, 2.85; N, 3.60%; Found: C, 43.38; H, 2.95; N,
3.67%.
4-Chloro-N-(2-oxo-2-(thiophen-3-yl)ethyl)benzenesulfonamide (3t): White solid (133 mg,
1
85%), mp: 119-120 °C; H NMR (CDCl3, 400 MHz): δ 8.09-8.08 (m, 1H), 7.84-7.81 (m, 2H),
7.47-7.44 (m, 3H), 7.36-7.34 (m, 1H), 5.74 (t, J = 8.8 Hz, 1H), 4.37 (d, J = 4.4 Hz, 2H); 13C{1H}
NMR (CDCl3, 100 MHz): δ 186.8, 139.6, 138.5, 137.9, 133.2, 129.6, 128.7, 127.4, 126.4, 49.3.
Anal. Calcd. For C12H10ClNO3S2: C, 45.64; H, 3.19; N, 4.44%; Found: C, 45.72; H, 3.28; N,
4.51%.
N-(2-Oxo-2-phenylethyl)benzenesulfonamide (3u):12 White solid (105 mg, 77%), mp: 40-41
1
°C; H NMR (CDCl3, 400 MHz): δ 7.91-7.89 (m, 2H), 7.86-7.83 (m, 2H), 7.63-7.45 (m, 6H),
5.69 (t, J = 8.4 Hz, 1H), 4.48 (d, J = 4.4 Hz, 2H); 13C{1H} NMR (CDCl3, 100 MHz): δ 192.6,
139.3, 134.6, 133.9, 133.1, 129.4, 129.1, 128.0, 127.3, 48.8.
N-(2-(4-(Tert-butyl)phenyl)-2-oxoethyl)benzenesulfonamide (3v): Yellow oil (137 mg, 83%);
1H NMR (CDCl3, 400 MHz): δ 7.91-7.88 (m, 2H), 7.79-7.77 (m, 2H), 7.55-7.46 (m, 5H), 5.71 (t,
J = 8.4 Hz, 1H), 4.45 (d, J = 4.4 Hz, 2H), 1.32 (s, 9H); 13C{1H} NMR (CDCl3, 100 MHz): δ
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192.1, 158.7, 139.3, 133.0, 131.3, 129.3, 128.0, 127.2, 126.1, 48.7, 35.4, 31.1. Anal. Calcd. For
C18H21NO3S: C, 65.23; H, 6.39; N, 4.23%; Found: C, 65.33; H, 6.30; N, 4.28%.
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2-Oxo-2-phenylethyl acetate (4a):18f White Solid (75 mg, 84%), mp: 42-43 °C; H NMR
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(CDCl3, 400 MHz): δ 7.91-7.88 (m, 2H), 7.61-7.57 (m, 1H), 7.49-7.45 (m, 2H), 5.32 (s, 2H),
2.21 (s, 3H); 13C{1H} NMR (CDCl3, 100 MHz): δ 192.3, 170.5, 134.3, 134.0, 129.0, 127.9, 66.2,
20.7.
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2-Oxo-2-(p-tolyl)ethyl acetate (4b):18f White Solid (78 mg, 81%), mp: 84-85 °C; H NMR
(CDCl3, 400 MHz): δ 7.80-7.78 (m, 2H), 7.27-7.25 (m, 2H), 5.30 (s, 2H), 2.40 (s, 3H), 2.20 (s,
2H); 13C{1H} NMR (CDCl3, 100 MHz): δ 191.8, 170.5, 144.9, 131.8, 129.6, 127.9, 66.0, 21.8,
20.6.
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2-(4-(Tert-butyl)phenyl)-2-oxoethyl acetate (4c):18b White Solid (100 mg, 86%); H NMR
(CDCl3, 400 MHz): δ 7.86-7.84 (m, 2H), 7.50-7.48 (m, 2H), 5.32 (s, 2H), 2.22 (s, 3H), 1.33 (s,
9H); 13C{1H} NMR (CDCl3, 100 MHz): δ 191.9, 170.6, 157.9, 131.7, 127.8, 125.9, 66.1, 35.3,
31.1, 20.7.
2-(3-Fluorophenyl)-2-oxoethyl acetate (4d): Yellowish oil (81 mg, 80%); 1H NMR (CDCl3, 400
MHz): δ 7.65-7.63 (m, 1H), 7.57-7.53 (m, 1H), 7.45-7.40 (m, 1H), 7.28-7.25 (m, 1H), 5.26 (s,
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2H), 2.16 (s, 3H); 13C{1H} NMR (CDCl3, 100 MHz): δ 191.2, 170.3, 162.8 (d, JC-F = 248 Hz),
136.1 (d, 3JC-F = 6 Hz), 130.6 (d, 3JC-F = 8 Hz), 123.5 (d, 4JC-F = 3 Hz), 120.9 (d, 2JC-F = 22 Hz),
114.5 (d, 2JC-F = 22 Hz), 66.0, 20.4. Anal. Calcd. For C10H9FO3: C, 61.23; H, 4.62%; Found: C,
61.29; H, 4.72%.
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2-(4-Bromophenyl)-2-oxoethyl acetate (4e):18f White Solid (94 mg, 73%), mp: 82-83 °C; H
NMR (CDCl3, 400 MHz): δ 7.78-7.76 (m, 2H), 7.64-7.62 (m, 2H), 5.28 (s, 2H), 2.22 (s, 3H);
13C{1H} NMR (CDCl3, 100 MHz): δ 191.5, 170.5, 133.1, 132.4, 130.0, 129.4, 65.9, 20.6.
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2-Oxo-2-(thiophen-3-yl)ethyl acetate (4f):18c Yellow Solid (77 mg, 84%), mp: 75-76 °C; H
NMR (CDCl3, 400 MHz): δ 8.10-8.09 (m, 1H), 7.53-7.51 (m, 1H), 7.36-7.34 (m, 1H), 5.19 (s,
2H), 2.20 (s, 3H); 13C{1H} NMR (CDCl3, 100 MHz): δ 186.8, 170.5, 138.7, 132.3, 126.9, 126.5,
66.3, 20.6.
Supporting information: Scanned copies of H and 13C NMR spectra of the synthesized
1
compounds, CIF file for compound 3l are available as supporting information. This material is
available free of charge via the Internet at http://pubs.acs.org.
Acknowledgements: A. Majee acknowledges financial support from the DST-RSF Major
Research Project (Ref. No. INT/RUS/RSF/P-08). S. Santra and G. V. Zyryanov acknowledge the
Russian Science Foundation – Russia (Ref. # 18-73-00301) for funding. We are thankful to the
DST-FIST and UGC-SAP programmes.
Author Information
Email
*Adinath Majee: adinath.majee@visva-bharati.ac.in (Corrresponding Author)
Sachinta Mahato: sachinto123@gmail.com
Sougata Santra: sougatasantra85@gmail.com
Grigory V. Zyryanov: gvzyryanov@gmail.com
ORCID
Adinath Majee: 0000-0002-5439-6851
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Sougata Santra: 0000-0002-4186-6105
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Grigory V. Zyryanov: 0000-0002-9692-2346
Notes
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The authors declare no competing financial interest.
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Brønsted Acidic Ionic Liquid-Catalyzed Tandem Reaction: An Efficient Approach
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N. K.; Zyryanov, G. V; Majee, A.; Charushin, V. N.; Chupakhin, O. N.; Santra, S.
Copper Nanoparticles as Inexpensive and Efficient Catalyst: A Valuable Contribution in
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