Water-Promoted Regiospecific Azidolysis and Copper-Catalyzed Azide-Alkyne Cycloaddition: One-Pot Synthesis of 3-Hydroxy-1-alkyl-3-[(4-aryl/alkyl-1H-1,2,3-triazol-1-yl)methyl]indolin-2-ones

Article abstract of DOI:10.1021/acs.joc.6b01819

An efficient, eco-friendly, base free, one-pot, sequential protocol was developed for epoxide azidolysis and copper-catalyzed azide-alkyne cycloaddition using water as the solvent for the synthesis of 3-hydroxy-1-alkyl-3-[(4-aryl/alkyl-1H-1,2,3-triazol-1-yl)methyl]indolin-2-ones. The optimized reaction conditions have been generalized in the case of aromatic as well as aliphatic alkyne partners to afford good yields and high regioselectivity.

Full text of DOI:10.1021/acs.joc.6b01819

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Article
Water Promoted Regiospecific Azidolysis and Copper Catalysed
Azide-Alkyne Cycloaddition: One-Pot Synthesis of 3-Hydroxy-1-
alkyl-3-[(4-aryl/alkyl-1H-1,2,3-triazol-1-yl)methyl]indolin-2-ones
Kapil Kumar, Debabrata Konar, Sandeep Goyal, Mukesh Gangar,
Mangilal Chouhan, Ravindra Kumar Rawal, and Vipin A Nair
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.6b01819 • Publication Date (Web): 22 Sep 2016
Downloaded from http://pubs.acs.org on September 23, 2016
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Page 1 of 10
The Journal of Organic Chemistry
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Water Promoted Regiospecific Azidolysis and Copper Catalysed Az-
ide-Alkyne Cycloaddition: One-Pot Synthesis of 3-Hydroxy-1-alkyl-
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3
-[(4-aryl/alkyl-1H-1,2,3-triazol-1-yl)methyl]indolin-2-ones
a,b
a
a
a
c
Kapil Kumar , Debabrata Konar , Sandeep Goyal , Mukesh Gangar , Mangilal Chouhan , Ravin-
b
a
dra K. Rawal *, Vipin A. Nair *
a
Department of Medicinal Chemistry, National Institute of Pharmaceutical Education and Research, Sector 67, SAS
b
Nagar, Punjab 160062, India; Department of Pharmaceutical Chemistry, Indo-Soviet Friendship College of Pharma-
cy (ISFCP), Moga, Punjab, 142001; Department of Pharmaceutical Sciences, Mohanlal Sukhadia University, Udai-
c
pur, Rajasthan, 313001, India.
Key words: Regioselectivity, water, click chemistry, 1,2,3-triazole.
ABSTRACT: An efficient, eco-friendly, base free, one-pot, sequential protocol was developed for epoxide azidolysis and
copper catalysed azide-alkyne cycloaddition using water as the solvent for the synthesis of 3-hydroxy-1-alkyl-3-[(4-
aryl/alkyl-1H-1,2,3-triazol-1-yl)methyl]indolin-2-ones. The optimised reaction condition has been generalised in the case
of aromatic as well as aliphatic alkyne partner affording good yields and high regioselectivity.
Introduction
3
-Substituted-indolin-2-ones such as convolutamydines,
diazonamide A, leptosin D, 3-hydroxyglucoisatisin, witin-
dolinone C, TMC-95, celogentin K and dioxibrassinine as
well as several other biologically active compounds are
widely found in nature and have demonstrated diverse
1
biological properties. Few natural products containing 3-
hydroxy oxindole scaffold are illustrated in Figure 1. The
activity of these molecules mainly resides in the substitu-
tion at the C-3 quaternary centre. Kumar et. al. estab-
lished the antimalarial, antitubercular and anti-protozoal
1
d-f
activity of 1H-1,2,3-triazole tethered with oxindole. Cop-
per-catalyzed azide–alkyne cycloaddition (CuAAC) or
Huisgen cycloaddition is one of the most important
methods for the formation of 1,4-disubstituted 1,2,3-
Figure 1. Natural products containing 3-hydroxy oxindole
scaffold.
Despite the wide applicability, the available methods have
limitations such as pre-synthesis of metal complex, long
reaction time, moderate yields, use of air and moisture
sensitive reagents or catalysts, lack of cost effectiveness
which provide sufficient scope for the development of
2
triazoles, with high efficiency, regioselectivity and excel-
lent atom economy. These molecules exhibit interesting
3
biological properties and have found numerous applica-
4
tions in various fields like bioconjugation, dendrimer
5
6
synthesis, surface science, combinatorial organic synthe-
better conditions. In continuation of our investigations on
7
8
19,20
sis as well as in material science.
3-substituted-indolin-2-ones
efforts were mainly fo-
Examination of the literature provides various synthetic
cused on the development of an eco-friendly one-pot se-
quential protocol for epoxide azidolysis and copper cata-
lysed cycloaddition reaction using water as the reaction
medium. The developed protocol afforded 3-hydroxy-1-
alkyl-3-[(4-aryl/alkyl-1H-1,2,3-triazol-1-yl)methyl]indolin-
2-ones with excellent yields and regioselectivity in a short
span of time.
9
modifications employing different metals such as Zn,
10
11
12
13
14
Ni, Ag, Ru, Ir, and ligands to protect the metal cen-
tre from disproportionation and oxidation, different cop-
15
per salts on solid supports and even without the use of
16
copper. Recently, transition metal nanoparticles were
found to serve as efficient catalysts for the synthesis of
17
this privileged scaffold. Furthermore one-pot multicom-
Results and Discussion
ponent reactions have proved their utility for regioselec-
18
The required oxirane derivatives were prepared as illus-
trated in Scheme 1. N-alkyl derivatives were synthesized
tive triazole synthesis.
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Page 2 of 10
by treating isatins with NaH and then reacting with me- 0.75 h affording 92% yield with a regiospecific oxirane
1
2
3
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5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
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3
3
3
3
3
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3
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4
4
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5
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5
6
thyl iodide or benzyl bromide, in dry DMF at room tem-
perature. Construction of epoxy ring at C-3 position of
isatin derivatives were realised by Corey-Chakovsky reac-
tion using trimethylsulfoxonium iodide and cesium car-
bonate in acetonitrile solvent at 50 C to afford good yield
of 3-epoxy-indolin-2-ones.
ring opening from the less hindered end. Further increase
in temperature did not improve the yield of the reaction.
From the above observation, we inferred that reacting 1.0
equivalent of 1-methylspiro[indoline-3,2'-oxiran]-2-one
and 1.2 equivalent of sodium azide in water at 50ºC would
be the most suitable condition for the reaction. The syn-
o
thesized
3-(azidomethyl)-3-hydroxy-1-methylindolin-2-
one were used in copper catalysed azide-alkyne cycload-
dition reaction. To investigate the reaction in detail, a
model reaction of phenylacetylene 5(i) and 3-
0
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2
3
4
5
6
7
8
9
0
1
2
3
4
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9
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5
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7
8
9
0
(
azidomethyl)-3-hydroxy-1- methylindolin-2-one 4a was
performed in the presence of different copper salts using
water as solvent at room temperature (Scheme 3).
Scheme 1. Synthesis of 3-epoxy-indolin-2-ones.
Based on our earlier work on water promoted epoxide
21
aminolysis, we decided to apply a similar strategy for the
synthesis of the azide partner required for azide-alkyne
cycloaddition reaction. For a detailed investigation, a
model
reaction
was
performed
with
1-
Scheme 3. Catalytic azide-alkyne cycloaddition reaction.
From the different copper salts employed, it was inferred
that CuI provided maximum yields of the product, in a
short reaction time, at an optimum catalyst concentration
of 10 mol% compared with CuCl and CuBr which provided
inferior results (Table 2).
methylspiro[indoline-3,2'-oxiran]-2-one 3a and sodium
azide in different solvents at room temperature, as illus-
trated in Scheme 2. Solvents like cyclohexane, toluene,
DMF, DMSO, DCM, 1,4-dioxane and THF did not afford
the product (Table 1), while an improvement was ob-
served with polar solvents. We envisaged that this may be
due to the better solubility of the sodium azide in polar
medium which serves as a nucleophile for opening of the
oxirane ring.
Table 2. Effect of different copper salts on azide-alkyne
a
cycloaddition reaction
b
Entry
Catalyst (10mol%)
CuBr
Cu(OAc)2
CuCl(I)
CuCl(II)
CuO
Time (h)
4.5
4.0
3.0
3.5
Yield (%)
1
2
3
4
5
6
82
84
87
78
68
90
5.0
0.5
CuI
a
Reaction
condition:
3-(azidomethyl)-3-hydroxy-1-
methylindolin-2-one (1.0 equiv), phenylacetylene (1.2 equiv.),
water (3 mL), temp. 30 C; isolated yield.
Scheme 2. Azidolysis of the 3-epoxy-indolin-2-one.
o
b
a
Table 1. Effect of solvents on azidolysis of oxirane ring
b
The effect of the solvent, as a reaction variable was also
evaluated. In the case of non-polar solvents like cyclohex-
ane and toluene, the reaction afforded unsatisfactory re-
sults compared to aprotic solvents like THF, DCM, ace-
tonitrile and chloroform (Table 3). Protic polar solvents
Entry
Solvent
Time(h) Yield (%)
1
2
3
Cyclohexane
Toluene
DMF
8
8
8
-
-
-
4
5
DMSO
DCM
8
8
-
-
t
like EtOH and BuOH afforded better yields. However
water was found to significantly enhance the reaction rate
affording the best yields of the desired product in 0.5h.
Table 3. Effect of solvent on copper catalysed azide-
6
7
8
9
10
11
1,4-dioxane
THF
8
8
4
2
12
0.75
0.75
0.75
-
-
EtOH
EtOH
42
60
65
92
93
92
c
a
alkyne cycloaddition reaction
b
H O
Entry
Solvent
Time (h) Yield (%)
2
c
H O
1
2
3
4
5
6
7
8
Toluene
Cyclohexane
Chloroform
THF
5
5
5
5
5
5
5
5
46
52
65
72
67
78
80
82
90
2
d
1
1
2
3
H O
2
e
H O
2
a
Reaction condition: 1-methylspiro[indolin-3,2'-oxiran]-2-one
1.0 equiv.), sodium azide (1.2 equiv.), temp. 30 C; isolated
yield; temp. 50°C; temp. 70 C; temp. 90 C.
o
b
(
DCM
c
d
o
e
o
Acetonitrile
EtOH
To evaluate our assumption, we tried water as the reac-
tion medium which afforded 65% of the desired product
at room temperature indicating an enhancement in the
reaction rate. Even then the reaction was slow consuming
t
BuOH
9
H O
2
0.5
a
Reaction
condition:
3-(azidomethyl)-3-hydroxy-1-
methylindolin-2-one (1.0 equiv), phenylacetylene (1.2 equiv.),
CuI (0.1 equiv.), temp. 30 C; isolated yield.
1
2 h for completion. A separate study demonstrated a
o
b
drastic rate enhancement at 50ºC attaining completion in
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The Journal of Organic Chemistry
The reaction mixture was then allowed to stir at room
To evaluate the prospect of both the reactions sequential-
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
ly, azidolysis of oxirane ring and copper catalysed cy-
cloaddition reaction were performed in one-pot without
isolating the intermediate 3-(azidomethyl)-3-hydroxy-1-
methylindolin-2-one derivative. A model reaction em-
ploying 1.0 equivalent of 1-methylspiro[indolin-3,2'-
oxiran]-2-one 3a and 1.2 equivalent of sodium azide in
water as solvent was heated at 50ºC for 0.75 h. The com-
pletion of the azidolysis was monitored by TLC analysis.
Thereafter, the reaction temperature was allowed to at-
tain room temperature and to this reaction mixture was
added 0.1 equivalent of CuI and 1.2 equivalent of phenyla-
cetylene 5(i) without isolating the 3-(azidomethyl)-3-
hydroxy-1-methylindolin-2-one 4a.
temperature for another 0.5 h. The progress of the reac-
tion was followed by TLC analysis. To our satisfaction, the
reaction afforded the desired 3-hydroxy-1-methyl-3-((4-
phenyl-1H-1,2,3-triazol-1-yl)methyl) indolin-2-one 6a(i)
with 82% yield (Table 4, entry 1). The scope of the opti-
mized one-pot protocol was further extended to different
3-epoxy-indolin-2-ones and phenylacetylene derivatives
bearing both electron withdrawing and donating groups.
The reaction afforded desired 1,4-disubstituted-1,2,3-
triazole derivatives (Scheme 4) in good to excellent yields
(Table 4). The optimized conditions were further extend-
ed to alkyne variants such as ethylpropiolate and 3-epoxy-
indolin-2-ones (Scheme 5) and found to afford the prod-
ucts in reasonably good yields (Table 5). To account for
the regioselective formation of 1,4-disubstituted-1,2,3-
triazole by azidolysis and azide-alkyne cycloaddition reac-
tion, we propose a plausible mechanism (Figure 2).
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Scheme 4. One-pot azidolysis and cycloaddition reactions
with aryl acetylenes.
Table 4. Generalisation of optimised condition for one-
pot epoxide azidolysis and azide-alkyne cycloaddition
Scheme 5. One-pot azidolysis and cycloaddition reactions
with alkynes.
a
reaction
b
En
try
1
R
R1
R2
H
Time
Prod-
uct
Yield (%)
Table 5. Generalisation of optimised conditions of one
a
(T /T )(h)
pot azidolysis and azide-alkyne cycloaddition reaction
1
2
b
H
Me
0.75/0.5
0.75/1.5
0.75/1.0
1.5/1.0
1.5/2.0
1.5/1.5
1.5/1.5
1.5/2.0
1.5/1.5
2.5/1.5
2.5/2.0
2.5/1.5
1.5/1.5
1.5/2.0
1.5/1.5
3.0/1.5
3.0/2.5
3.0/1.5
1.5/1.0
1.5/1.5
1.5/1.0
2.5/1.0
2.5/1.5
2.5/1.0
3.0/1.5
3.0/2.0
3.0/1.5
6a(i)
82
76
79
78
72
76
77
75
78
76
70
73
80
76
78
76
72
69
78
73
75
75
72
74
78
73
75
Entry
R
R1 Time(T /T )(h) Product
Yield (%)
1
2
2
3
4
5
6
7
8
9
H
H
H
H
Me Br
Me OMe
6a(ii)
6a(iii)
6b(i)
6b(ii)
6b(iii)
6c(i)
6c(ii)
6c(iii)
6d(i)
6d(ii)
6d(iii)
6e(i)
6e(ii)
6e(iii)
6f(i)
6f(ii)
6f(iii)
6g(i)
1
H
H
Cl
Cl
Br
Br
OMe
Me
Me
Me
Bn
Me
Bn
Me
Bn
Me
Me
Bn
0.75/1.0
7a
7b
7c
7d
7e
7f
7g
7h
7i
78
72
76
68
73
66
76
74
69
2
3
4
5
6
7
8
1.5/2.5
1.5/1.5
2.5/3.0
1.5/1.5
3.0/4.0
1.5/1.5
2.5/1.5
3.0/2.5
Bn
H
Bn Br
Bn OMe
H
Cl
Cl
Cl
Cl
Cl
Cl
Br
Br
Br
Br
Br
Br
Me
H
Me Br
Me OMe
10
Bn
H
9
11
Bn Br
Bn OMe
a
Reaction condition: 3-epoxy-indolin-2-one (1.0 equiv.),
sodium azide (1.2 equiv.), ethylpropiolate (1.2 equiv.), CuI (0.1
12
13
14
15
Me
H
o
b
equiv.), temp. 30 C, overall isolated yield, T = time for epox-
1
Me Br
Me OMe
ide azidolysis, T = time for CuAAC reaction.
2
16
17
18
19
Bn
H
In the azidolysis reaction, water can be envisioned to ac-
tivate the reactant by hydrogen bonding thereby enhanc-
ing the electrophilicity of the oxirane ring to overcome
the energy barrier to facilitate a nucleophilic attack by the
azide. The azide would attack the least hindered end of
the oxirane ring providing high regioselectivity for the
reaction. Further in the azide-alkyne cycloaddition reac-
tion also water would activate the substrate to form the
intermediate I which coordinates with the copper salt to
afford the intermediate II. Thereafter the alkyne coordi-
nates to copper via a π-complex, and subsequently gener-
ates the intermediate III. The terminal nitrogen N1 attacks
the alkyne via a six membered cyclic transition state to
form the intermediate IV. Finally a reductive elimination
yields the intermediate V which affords the desired 1,4-
disubstituted-1,2,3-triazole, regenerating the copper cata-
lyst for another catalytic cycle.
Bn Br
Bn OMe
OMe Me
OMe Me Br
OMe Me OMe
Me
Me
Me
Me
Me
Me
H
2
2
2
2
2
2
2
2
0
6g(ii)
6g(iii)
6h(i)
6h(ii)
6h(iii)
6i(i)
1
2
3
4
5
6
7
Me
H
Me Br
Me OMe
Bn
H
Bn Br
Bn OMe
6i(ii)
6i(iii)
a
Reaction condition: 3-epoxy-indolin-2-one (1.0 equiv.), sodi-
um azide (1.2 equiv.), phenylacetylene (1.2 equiv.), CuI (0.1
equiv.), temp. 30 C, overall isolated yield, T = time for epox-
o
b
1
ide azidolysis, T = time for CuAAC reaction.
2
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To conclude, an eco-friendly one-pot sequential protocol
Typical procedure for spiro[indoline-3,2'-oxiran]-2-
one formation
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
was developed for epoxide azidolysis and copper cata-
lysed azide-alkyne cycloaddition using water as the reac-
tion medium. The developed protocol demonstrated regi-
oselectivity in both azidolysis of oxirane derivatives and
CuAAC reactions where opening of the oxirane ring from
the less substituted end followed by regioselective for-
mation of 1,4-disubstituted-1,2,3- triazole was observed.
The optimized reaction condition was extended to obtain
A mixture of trimethylsulfoxonium iodide (1.0 mmol) and
cesium carbonate (2.0 mmol) in dry acetonitrile was
o
stirred at 50 C for 1 h under nitrogen atmosphere to gen-
erate the sulphur ylide. To this, a solution of isatin (1.0
mmol) in dry acetonitrile (5 mL) was added dropwise over
10 min. The progress of the reaction was monitored by
TLC. After completion, the reaction mixture was filtered
through a celite-bed and the filtrate was evaporated to
dryness. The crude product thus obtained was purified by
column chromatography on silica gel (60–120mesh) using
EtOAc: hexane (05:95) mixture as the eluent to afford the
pure product.
3
-hydroxy-1-alkyl-3-[(4-aryl/alkyl-1H-1,2,3-triazol-1-
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
yl)methyl]indolin-2-one derivatives with good to excel-
lent yields. The present method has advantages over pre-
viously reported methods such as an environmental be-
nign protocol, catalytic use of readily available and inex-
pensive CuI, simplicity of the reaction condition, base free
and short reaction time with high regioselectivity.
1-Methylspiro[indolin-3,2'-oxiran]-2-one (3a)
Pale yellow solid; mp 84-86◦C; Yield: 0.13g, 78%; 1H NMR
(CDCl3, 400 MHz) δ 7.41-7.37 (m, 1H), 7.13-7.07 (m, 2H),
6.93 (d, 1H, J = 7.8Hz), 3.59 (d, 1H, J = 6.7Hz), 3.44 (d, 1H, J
= 6.7Hz), 3.28 (s, 3H); 13C NMR (CDCl3, 100MHz) δ 171.8,
145.1, 130.4, 122.9, 122.7, 122.1, 108.8, 56.4, 54.1, 26.6; ESI-
+
HRMS(m/z): [M+Na] calcd. for C H NNaO , 198.0531,
1
0
9
2
found 198.0527.
1-Benzylspiro[indolin-3,2'-oxiran]-2-one (3b)
Pale orange solid; mp 114-116 C; Yield: 0.19g, 75%; H NMR
◦
1
(CDCl , 400 MHz) δ 7.37-7.26 (m, 6H), 7.15-7.13 (m, 1H),
3
7.08-7.04 (m, 1H), 6.84 (d, 1H, J = 7.9Hz), 4.98 (q, 2H, J =
11.4, 15.7Hz), 3.67 (d, 1H, J = 6.7Hz), 3.50 (d, 1H, J = 6.7Hz);
1
3
C NMR (CDCl , 100MHz) δ 171.9, 144.3, 135.4, 130.4, 128.9,
3
127.9, 127.4, 123.0, 122.7, 122.2, 109.9, 56.4, 56.3, 44.3; ESI-
+
HRMS(m/z): [M+Na] calcd. for C H NNaO , 274.0844,
1
6
13
2
found 274.0840.
5-Chloro-1-methylspiro[indolin-3,2'-oxiran]-2-one (3c)
◦
1
Pale yellow solid; mp 163-165 C; Yield: 0.16g, 75%; H NMR
(CDCl , 400 MHz) δ 7.40-7.37 (m, 1H), 7.11 (d, 1H, J =
3
2.1Hz), 6.87 (d, 1H, J = 8.3Hz), 3.62 (d, 1H, J = 6.7Hz), 3.45
1
3
(d, 1H, J = 6.7Hz), 3.30 (s, 3H); C NMR (CDCl , 100MHz)
3
δ 171.3, 143.6, 130.3, 128.5, 124.5, 122.6, 109.8, 56.2, 54.2, 26.8;
+
ESI-HRMS(m/z): [M+Na] calcd.
232.0141, found 232.0134.
for C H ClNNaO ,
10 8 2
Figure 2. Plausible mechanism.
1-Benzyl-5-chlorospiro[indolin-3,2'-oxiran]-2-one (3d)
◦
1
Brownish solid; mp 144-148 C; Yield: 0.20g, 72%; H NMR
EXPERIMENTAL SECTION
(CDCl , 400 MHz) δ 7.38-7.31 (m, 5H), 7.26-7.24 (m, 1H),
3
1
13
7.12 (d, 1H, J = 2.1Hz), 6.74 (d, 1H, J = 8.4Hz), 4.98 (q, 2H, J
= 5.7, 15.7Hz), 3.69 (d, 1H, J = 6.7Hz), 3.49 (d, 1H, J =
The H NMR and C NMR spectra were recorded in deu-
teriated solvent (CDCl /DMSO) using TMS as the internal
3
1
3
6.7Hz); C NMR (CDCl , 100MHz) δ 171.4, 142.7, 134.9,
standard. The chemical shifts (δ) are given in ppm relative
to residual signal of the solvents. Coupling constants are
given in Hz. The following abbreviations are used to indi-
cate the multiplicity: s, singlet; d, doublet; t, triplet; q,
quartet; m, multiplet; dd, double doublet; brs, broad sin-
glet signal. HRMS spectra were recorded on Bruker Maxix
TOF spectrometer. Melting points were recorded and
uncorrected. All the starting materials [isatin, 5-chloro
isatin, 5-bromo isatin, 5-methoxy isatin, 5-methyl isatin],
benzyl bromide, methyl iodide, trimethylsulphoxonium
iodide, phenylacetylene, 4-bromo phenylacetylene, 4-
methoxyphenylacetylene, ethylpropiolate, copper-iodide,
cesium-carbonate were purchased from commercial
sources and used as such without further purification.
3
130.2, 129.0, 128.6, 128.0, 127.4, 124.5, 122.7, 110.9, 56.2, 54.5,
+
44.4; ESI-HRMS(m/z): [M+Na] calcd. for C H ClNNaO ,
16 12
2
308.0454, found 308.0446.
5-Bromo-1-methylspiro[indolin-3,2'-oxiran]-2-one
(3e)
◦
1
Brownish solid; mp 167-169 C; Yield: 0.19g, 74%; H NMR
(CDCl , 400 MHz) δ 7.55-7.52 (m, 1H), 7.29-7.24 (m, 1H),
3
6.83 (d, 1H, J = 8.3Hz), 3.61 (d, 1H, J = 6.6Hz), 3.45 (d, 1H, J
1
3
= 6.7Hz), 3.29 (s, 3H); C NMR (CDCl , 100MHz) δ 171.2,
3
144.1, 133.2, 125.4, 124.8, 115.6, 110.3, 56.0, 54.2, 26.8; ESI-
+
HRMS(m/z): [M+Na] calcd. for C H BrNNaO , 275.9636,
10
8
2
found 275.9623.
1-Benzyl-5-bromospiro[indolin-3,2'-oxiran]-2-one (3f)
◦
1
Reddish solid; mp 150-152 C; Yield: 0.23g, 70%; H NMR
CDCl , 400 MHz) δ 7.41-7.28 (m, 6H), 7.25 (d, 1H, J =
(
3
ACS Paragon Plus Environment

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The Journal of Organic Chemistry
+
1
3
.9Hz), 6.70 (d, 1H, J = 8.3Hz), 4.98 (q, 2H, J = 4.8, 15.7Hz), HRMS(m/z): [M+H] calcd. for C H N O , 321.1352,
1
8
17
4
2
1
3
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
.68 (d, 1H, J = 6.7Hz), 3.49 (d, 1H, J = 6.7Hz); C NMR
found 321.1338.
(
CDCl , 100MHz) δ 171.3, 143.2, 134.8, 133.1, 129.0, 128.0,
3-((4-(4-Bromophenyl)-1H-1,2,3-triazol-1-yl)methyl)-3-
3
1
27.4, 125.5, 124.9, 115.7, 111.4, 56.0, 54.5, 44.4; ESI-
hydroxy-1-methyl indolin-2-one [6a(ii)]
White solid; mp 167-169 C; Yield: 0.30g, 76%; H NMR
+
◦
1
HRMS(m/z): [M+Na] calcd. for C H BrNNaO , 351.9949,
1
6
12
2
found 351.9918.
-Methoxy-1-methylspiro[indolin-3,2'-oxiran]-2-one
3g)
Brownish solid; mp 144-146 C; Yield: 0.14g, 70%; H NMR
CDCl , 400 MHz) δ 6.93 (dd, 1H, J = 2.5, 6.0Hz), 6.85 (d,
(CDCl , 400 MHz) δ 8.00 (s, 1H), 7.75-7.71 (m, 2H), 7.59-
3
5
(
7.56 (m, 2H), 7.39-7.35(m, 1H), 7.08-7.04 (m, 1H), 6.87-
6.80 (m, 2H), 4.81 (d, 1H, J = 14.2Hz), 4.75 (d, 1H, J =
◦
1
13
14.2Hz), 3.60 (brs, 1H), 3.22 (s, 3H); C NMR (DMSO-d ,
6
(
100MHz) δ 175.5, 145.2, 143.7, 132.3, 130.3, 128.6, 127.6, 124.7,
3
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
H, J = 8.5), 6.74 (d, 1H, J = 2.5Hz), 3.81 (s, 3H), 3.60 (d, 1H,
123.5, 122.8, 121.3, 109.2, 74.7, 55.0, 26.5; ESI-HRMS(m/z):
1
3
+
J = 6.7Hz), 3.43 (d, 1H, J = 6.7Hz), 3.28 (s, 3H); C NMR
CDCl , 100MHz) δ 171.5, 156.3, 138.4, 124.0, 115.1, 109.4,
[M+H] calcd.
399.0445.
for C H BrN O , 399.0457, found
18 16 4 2
(
3
+
1
09.1, 56.7, 55.9, 54.2, 26.7; ESI-HRMS(m/z): [M+Na]
3-Hydroxy-3-((4-(4-methoxyphenyl)-1H-1,2,3-triazol-1-
yl)methyl)-1-methylindolin-2-one [6a(iii)]
calcd. for C H NNaO , 228.0637, found 228.0638.
1,5-Dimethylspiro[indolin-3,2'-oxiran]-2-one (3h)
Brownish solid; mp 118-120 C; Yield: 0.13g, 68%; H NMR
(CDCl , 400 MHz) δ 7.19 (d, 1H, J = 0.9Hz), 6.95-6.94 (m,
1H), 6.83 (d, 1H, J = 7.9Hz), 3.59 (d, 1H, J = 6.7Hz), 3.43 (d,
1H, J = 6.7Hz), 3.28 (s, 3H), 2.35 (s, 3H); C NMR (CDCl ,
100MHz) δ 171.7, 142.7, 132.6, 130.6, 122.8, 122.7, 108.6, 56.5,
54.0, 26.7, 21.0; ESI-HRMS(m/z): [M+Na] calcd. for
C H NNaO , 212.0687, found 212.0681.
1-Benzyl-5-methylspiro[indolin-3,2'-oxiran]-2-one (3i)
White solid; mp 148-150 C; Yield: 0.17g, 65%; H NMR
(CDCl , 400 MHz) δ 7.35-7.28 (m, 5H), 7.09-7.07 (m, 1H),
6.96 (s, 1H), 6.72 (d, 1H, J = 8.0Hz), 4.97 (q, 2H, J = 7.9,
15.6Hz), 3.67 (d, 1H, J = 6.7Hz), 3.48 (d, 1H, J = 6.7Hz), 2.31
(s, 3H); C NMR (CDCl , 100MHz) δ 171.9, 141.9, 135.4,
132.6, 130.6, 128.8, 127.8, 127.4, 122.9, 122.7, 109.7, 56.4,
54.2, 44.3, 20.9; ESI-HRMS(m/z): [M+Na] calcd. for
1
1
11
3
◦
1
Yellow solid; mp 186-188 C; Yield: 0.28g, 79%; H NMR
◦
1
(CDCl , 400 MHz) δ 7.93 (s, 1H), 7.76 (d, 2H, J = 8.7Hz),
3
7.36-7.28 (m, 1H), 7.04-7.01 (m, 1H), 6.97 (d, 2H, J =
8.7Hz), 6.84-6.78 (m, 2H), 4.80 (d, 1H, J = 14.1Hz), 4.71 (d,
3
1
3
13
1H, J = 14.2Hz), 4.18 (brs, 1H), 3.86 (s, 3H), 3.20 (s, 3H); C
3
NMR (CDCl , 100MHz) δ 175.4, 159.7, 147.5, 143.0, 130.7,
3
+
127.1, 126.8, 124.6, 123.7, 123.0, 120.7, 114.2, 108.9, 75.2, 55.3,
+
55.3, 26.5; ESI-HRMS(m/z): [M+H] calcd. for C H N O ,
1
1
11
2
19 19
4
3
351.1457, found 351.1450.
1-Benzyl-3-hydroxy-3-((4-phenyl-1H-1,2,3-triazol-1-
◦
1
yl)methyl)indolin-2-one [6b(i)]
White solid; mp 169-171 C; Yield: 0.31g, 78%; H NMR
3
◦
1
(CDCl , 400 MHz) δ 7.93 (s, 1H), 7.83 (d, 2H, J = 7.4Hz),
3
1
3
7.46-7.35 (m, 3H), 7.26-7.22 (m, 6H), 7.03 (t, 1H, J =
7.6Hz), 6.91 (d, 1H, J = 7.4Hz), 6.73 (d, 1H, J = 7.9Hz), 5.00
(d, 1H, J = 15.6Hz), 4.92 (d, 1H, J = 14.0Hz), 4.80 (t, 2H, J =
3
+
1
3
C H NNaO , 288.1000, found 288.0993.
15.6Hz), 3.59 (brs, 1H); C NMR (DMSO-d , 100MHz) δ
1
7
15
2
6
Typical procedure for Synthesis of 3-hydroxy-1-alkyl-
3-[(4-aryl/alkyl-1H-1,2,3-triazol-1-yl)methyl]indolin-2-
one derivatives
A mixture of oxindole oxirane (1.0 mmol) and sodium
azide (1.2 mmol) were stirred in water at 50 C. The pro-
175.7, 146.3, 142.9, 136.3, 131.0, 130.3, 129.4, 129.0, 128.6,
128.4, 127.8, 127.5, 125.6, 125.1, 123.0, 109.9, 75.0, 54.8, 43.2;
+
ESI-HRMS(m/z): [M+H] calcd. for C H N O , 397.1665,
24
21
4
2
found 397.1659.
1-Benzyl-3-((4-(4-bromophenyl)-1H-1,2,3-triazol-1-
o
gress of reaction was monitored by TLC. After complete
consumption of oxirane, reaction mixture was cooled to
room temperature and to this CuI (10 mol%) and phenyl
acetylene/ethylpropiolate (1.2 mmol) were added. After
completion, the reaction mixture was washed with water
and extracted with ethyl acetate(3x20 mL). The combined
organic layers were dried over anhydrous Na SO and
washed with brine and evaporated under reduced pres-
sure to dryness. The crude product thus obtained was
purified by column chromatography on activated silica
gel (60-120 mesh) using dichloromethane:methanol
(99:01) solvent mixture as the eluent to afford the pure
product.
yl)methyl)-3-hydroxyindolin-2-one [6b(ii)]
White solid; mp 172-174 C; Yield: 0.34g, 72%; H NMR
◦
1
(CDCl , 400 MHz) δ 7.94 (s, 1H), 7.70-7.67 (m, 2H), 7.57-
3
7.54 (m, 2H), 7.27-7.18 (m, 6H), 7.06-7.02 (m, 1H), 6.92-
6.90 (m, 1H), 6.73 (d, 1H, J = 7.9Hz), 5.00 (d, 1H, J =
15.7Hz), 4.90 (d, 1H, J = 14.1Hz), 4.80 (q, 2H, J = 9.4,
1
3
15.7Hz), 3.74 (brs, 1H); C NMR (CDCl , 100MHz) δ 175.3,
2
4
3
146.7, 142.4, 134.7, 132.0, 130.9, 129.2, 129.0, 128.0, 127.3,
127.1, 126.6, 124.7, 123.8, 122.2, 121.4, 110.1, 75.2, 55.3, 44.1;
+
ESI-HRMS(m/z): [M+H] calcd.
475.0770, found 475.0756.
for C H BrN O ,
24 20 4 2
1-Benzyl-3-hydroxy-3-((4-(4-methoxyphenyl)-1H-1,2,3-
triazol-1-yl)methyl)indolin-2-one [6b(iii)]
Yellow solid; mp 138-140 C; Yield: 0.32g, 76%; H NMR
◦
1
3-Hydroxy-1-methyl-3-((4-phenyl-1H-1,2,3-triazol-1-
yl)methyl)indolin-2-one [6a(i)]
White solid; mp 156-158 C; Yield: 0.26g, 82%; H NMR
(CDCl , 400 MHz) δ 8.02 (s, 1H), 7.86-7.84 (m, 2H), 7.46-
7.43 (m, 2H), 7.38-7.33 (m, 2H), 7.04-7.02 (m, 1H), 6.85-
(CDCl , 400 MHz) δ 7.86 (s, 1H), 7.75 (d, 2H, J = 8.8Hz),
3
◦
1
7.27-7.18 (m, 6H), 7.04-6.96 (m, 3H), 6.90 (d, 1H, J =
6.9Hz), 6.71 (d, 1H, J = 7.9Hz), 5.00 (d, 1H, J = 15.9Hz),
4.90 (d, 1H, J = 14.1Hz), 4.79 (q, 2H, J = 2.0, 13.6Hz), 3.92
3
1
3
6.78 (m, 2H), 4.83 (d, 1H, J = 14.2Hz), 4.74 (d, 1H, J =
14.2Hz), 4.04 (brs, 1H), 3.21 (s, 3H); C NMR (CDCl3,
(brs, 1H), 3.87 (s, 3H); C NMR (CDCl , 100MHz) δ 175.3,
3
1
3
159.7, 142.4, 134.8, 130.8, 129.0, 127.9, 127.1, 126.7, 124.7,
123.8, 123.0, 120.5, 114.2, 110.0, 93.3, 75.2, 55.4, 55.2, 44.1;
1
1
00MHz) δ 175.2, 147.7, 143.0, 130.8, 130.3, 128.9, 128.3,
26.7, 125.8, 124.6, 123.8, 121.5, 108.9, 75.2, 55.4, 26.5; ESI-
+
ESI-HRMS(m/z): [M+H] calcd. for C H N O , 427.1770,
25 23
4
3
found 427.1763.
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 6 of 10
◦
1
5
-Chloro-3-hydroxy-1-methyl-3-((4-phenyl-1H-1,2,3-
White solid; mp 198-200 C; Yield: 0.34g, 73%; H NMR
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
triazol-1-yl)methyl) indolin-2-one [6c(i)]
(CDCl , 400 MHz) δ 7.80 (s, 1H), 7.75-7.73 (m, 2H), 7.32-
3
◦
1
White solid; mp 226-228 C; Yield: 0.27g, 77%; H NMR
CDCl , 400 MHz) δ 7.92 (s, 1H), 7.86-7.84 (m, 2H), 7.47-
7.31 (m, 1H), 7.25-7.21 (m, 3H), 7.16-7.15 (m, 2H), 7.02 (d,
1H, J = 2.0Hz), 6.97 (d, 2H, J = 8.8Hz), 6.61 (d, 1H, J =
8.4Hz), 4.97 (d, 1H, J = 15.7Hz), 4.85 (q, 2H, J = 14.0,
(
3
7.44 (m, 2H), 7.39-7.33 (m, 2H), 6.92 (d, 1H, J = 2.0Hz),
6
=
.77 (d, 1H, J = 8.4Hz), 4.81 (d, 1H, J = 14.1Hz), 4.75 (d, 1H, J
14.1Hz), 3.66 (brs, 1H), 3.20 (s, 3H); C NMR (DMSO-d ,
16.1Hz), 4.74 (d, 1H, J = 15.7Hz), 3.87 (s, 3H), 3.86 (brs, 1H);
1
3
13
C NMR (DMSO-d , 100MHz) δ 175.3, 159.5, 146.3, 142.2,
6
6
1
1
00MHz) δ 175.2, 146.3, 142.7, 130.8, 130.5, 130.1, 129.4, 128.4,
135.9, 132.9, 131.1, 129.0, 128.1, 127.8, 127.4, 127.0, 123.5, 122.1,
114.8, 114.8, 111.9, 75.0, 55.6, 55.3, 43.2; ESI-HRMS(m/z):
26.9, 125.6, 125.0, 123.1, 110.8, 74.9, 54.5, 26.6; ESI-
+
+
HRMS(m/z): [M+H] calcd. for C H ClN O , 355.0962,
[M+H] calcd. for C H ClN O , 461.1380, found 461.1371.
1
8
16
4
2
25 22
4
3
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
found 355.0956.
-((4-(4-Bromophenyl)-1H-1,2,3-triazol-1-yl)methyl)-5-
chloro-3-hydroxy-1-methylindolin-2-one [6c(ii)]
5-Bromo-3-hydroxy-1-methyl-3-((4-phenyl-1H-1,2,3-
3
triazol-1-yl)methyl) indolin-2-one [6e(i)]
White solid; mp 238-240 C; Yield: 0.32g, 80%; H NMR
◦
1
◦
1
White solid; mp 218-220 C; Yield: 0.32g, 75%; H NMR
CDCl , 400 MHz) δ 7.96 (m, 1H), 7.87-7.83 (m, 2H), 7.50-
(CDCl , 400 MHz) δ 7.96 (m, 1H), 7.87-7.83 (m, 2H), 7.50-
3
(
7.34 (m, 4H), 7.06-7.04 (m, 1H), 6.86-6.81 (m, 1H), 4.81-
3
1
3
7.34 (m, 3H), 7.06-7.04 (m, 1H), 6.86-6.81 (m, 1H), 4.81-
4.76 (m, 2H), 3.18 (s, 3H), 3.11 (brs, 1H); C NMR (DMSO-
d6, 100MHz) δ 175.1, 146.3, 143.1, 132.9, 131.0, 129.4, 128.4,
127.7, 125.6, 123.2, 114.5, 111.3, 110.0, 74.8, 54.6, 26.6; ESI-
1
3
4.76 (m, 2H), 3.18 (s, 3H), 3.11 (brs, 1H); C NMR (DMSO-
d6, 100MHz) δ 179.9, 150.0, 147.4, 137.1, 135.4, 135.0, 134.8,
132.4, 131.6, 129.7, 128.3, 126.1, 115.5, 79.6, 59.4, 31.4; ESI-
+
HRMS(m/z): [M+H] calcd. for C H BrN O , 399.0457,
1
8
16
4
2
+
HRMS(m/z): [M+H] calcd. for C H BrClN O , 433.0067,
found 399.0448.
5-Bromo-3-((4-(4-bromophenyl)-1H-1,2,3-triazol-1-
1
8
15
4
2
found 433.0064.
5-Chloro-3-hydroxy-3-((4-(4-methoxyphenyl)-1H-1,2,3-
yl)methyl)-3-hydroxy-1-methylindolin-2-one [6e(ii)]
◦
1
triazol-1-yl)methyl) -1-methylindolin-2-one [6c(iii)]
White solid; mp 224-226 C; Yield: 0.36g, 76%; H NMR
◦
1
White solid; mp 198-200 C; Yield: 0.30g, 78%; H NMR
(CDCl , 400 MHz) δ 8.00-7.94 (m, 1H), 7.74-7.70 (m, 2H),
3
(CDCl , 400 MHz) δ 7.85 (s, 1H), 7.75 (d, 2H, J = 8.8Hz),
7.58-7.54 (m, 2H), 7.51-7.49 (m, 1H), 7.07-7.06 (m, 1H),
3
7.34-7.31 (m, 1H), 6.97 (d, 2H, J = 8.8Hz), 6.92 (d, 1H, J =
2.0Hz), 6.75 (d, 1H, J = 8.4Hz), 4.79 (d, 1H, J = 14.2Hz), 4.73
(d, 1H, J = 14.2Hz), 3.86 (s, 3H), 3.18 (s, 3H); C NMR
6.73 (d, 1H, J = 8.3Hz), 4.82-4.73 (m, 2H), 3.86 (brs, 1H),
1
3
3.18 (s, 3H); C NMR (CDCl , 100MHz) δ 175.2, 146.6, 140.6,
3
1
3
133.5, 132.0, 131.0, 129.4, 127.3, 126.7, 125.3, 122.1, 121.6, 108.7,
+
(CDCl , 100MHz) δ 174.7, 159.8, 147.7, 141.6, 130.7, 129.2,
75.2, 55.4, 21.1; ESI-HRMS(m/z): [M+H] calcd.
C H Br N O , 476.9562, found 476.9550.
for
3
128.4, 127.1, 125.2, 122.9, 120.6, 114.3, 109.9, 75.1, 60.4, 55.1,
1
8
15
2
4
2
+
26.6; ESI-HRMS(m/z): [M+H] calcd. for C H ClN O ,
5-Bromo-3-hydroxy-3-((4-(4-methoxyphenyl)-1H-1,2,3-
1
9
18
4
3
385.1067, found 385.1062.
1-Benzyl-5-chloro-3-hydroxy-3-((4-phenyl-1H-1,2,3-
triazol-1-yl)methyl) -1-methylindolin-2-one [6e(iii)]
◦
1
Yellow solid; mp 166-168 C; Yield: 0.33g, 78%; H NMR
triazol-1-yl)methyl) indolin-2-one [6d(i)]
(CDCl , 400 MHz) δ 7.85 (s, 1H), 7.77-7.72 (m, 2H), 7.48-
3
◦
1
White solid; mp 177-179 C; Yield: 0.33g, 76%; H NMR
7.64 (m, 1H), 7.06 (d, 1H, J = 1.9Hz), 6.98-6.94 (m, 2H),
6.69 (d, 1H, J = 8.3Hz), 4.80-4.72 (m, 2H), 4.31 (brs, 1H),
(CDCl , 400 MHz) δ 7.90 (s, 1H), 7.82-7.80 (m, 2H), 7.46-
3
1
3
7.42 (m, 2H), 7.39-7.35 (m, 1H), 7.24-7.19 (m, 4H), 7.15-7.13
(m, 2H), 7.02 (d, 1H, J = 2.1Hz), 6.61 (d, 1H, J = 8.4Hz), 4.97
(d, 1H, J = 15.7Hz), 4.87 (q, 2H, J = 11.2, 14.1Hz), 4.73 (d, 1H,
3.86 (s, 3H), 3.16 (s, 3H); C NMR (CDCl , 100MHz) δ
3
174.8, 159.7, 147.6, 142.1, 133.5, 128.8, 128.0, 127.1, 122.8,
120.7, 116.3, 114.3, 110.4, 75.1, 55.4, 55.1, 29.7; ESI-
1
3
+
J = 15.7Hz), 4.02 (brs, 1H); C NMR (CDCl , 100MHz) δ
HRMS(m/z): [M+H] calcd. for C H BrN O , 429.0562,
3
19 18
4
3
175.0, 147.8, 140.9, 134.2, 130.7, 130.1, 129.3, 129.0, 128.9,
128.4, 128.3, 128.1, 127.0, 125.8, 125.3, 121.2, 111.1, 75.2, 55.0,
found 429.0556.
1-Benzyl-5-bromo-3-hydroxy-3-((4-phenyl-1H-1,2,3-
+
44.3; ESI-HRMS(m/z): [M+H] calcd. for C H ClN O ,
triazol-1-yl)methyl) indolin-2-one [6f(i)]
White solid; mp 182-184 C; Yield: 0.36g, 76%; H NMR
2
4
20
4
2
◦
1
431.1275, found 431.1270.
1-Benzyl-3-((4-(4-bromophenyl)-1H-1,2,3-triazol-1-
yl)methyl)-5-chloro-3-hydroxyindolin-2-one [6d(ii)]
(CDCl , 400 MHz) δ 7.88 (s, 1H), 7.82 (d, 2H, J = 7.2Hz),
3
7.46-7.32 (m, 5H), 7.24-7.14 (m, 5H), 6.56 (d, 1H, J =
8.4Hz), 4.96 (d, 1H, J = 15.7Hz), 4.87 (q, 2H, J = 4.1, 14.1Hz),
◦
1
White solid; mp 196-198 C; Yield: 0.36g, 70%; H NMR
1
3
(CDCl , 400 MHz) δ 7.91 (s, 1H), 7.68-7.66 (m, 2H), 7.56-
4.73 (d, 1H, J = 15.7Hz); C NMR (DMSO-d , 100MHz) δ
3
6
7.54 (m, 2H), 7.35-7.32 (m, 1H), 7.25-7.21 (m, 3H), 7.14-7.12
(m, 2H), 7.02 (d, 1H, J = 2.0Hz), 6.64-6.60 (m, 1H), 4.96 (d,
1H, J = 15.7Hz), 4.86 (q, 2H, J = 4.1, 14.1Hz), 4.71 (d, 1H, J =
175.3, 146.4, 142.2, 135.7, 133.0, 131.0, 130.8, 129.4, 129.0,
128.5, 128.1, 127.8, 127.4, 125.6, 123.0, 114.9, 111.9, 75.0, 54.3,
+
43.3; ESI-HRMS(m/z): [M+H] calcd. for C H BrN O ,
24
20
4
2
1
3
15.7Hz), 4.27 (brs, 1H); C NMR (CDCl , 100MHz) δ 175.1,
475.0770, found 475.0768.
1-Benzyl-5-bromo-3-((4-(4-bromophenyl)-1H-1,2,3-
triazol-1-yl)methyl)-3-hydroxyindolin-2-one [6f(ii)]
3
146.8, 140.8, 134.2, 132.0, 130.7, 129.3, 129.0, 128.4, 128.1,
127.3, 127.0, 125.3, 124.1, 122.3, 121.4, 111.1, 75.2, 55.1, 44.2; ESI-
+
◦
1
HRMS(m/z): [M+H] calcd. for C H BrClN O , 509.0380,
White solid; mp 198-200 C; Yield: 0.40g, 72%; H NMR
24
19
4
2
found 509.0373.
1-Benzyl-5-chloro-3-hydroxy-3-((4-(4-
methoxyphenyl)-1H-1,2,3-triazol-1-yl)methyl)indolin-
-one [6d(iii)]
(CDCl , 400 MHz) δ 7.89 (s, 1H), 7.68 (d, 2H, J = 8.5Hz),
3
7.57-7.55 (m, 2H), 7.36 (dd, 1H, J = 1.9, 2.0Hz), 7.24-7.23
(m, 3H), 7.17-7.12 (m, 3H), 6.57 (d, 1H, J = 8.4Hz), 4.96 (d,
1H, J = 15.8Hz), 4.86 (q, 2H, J = 4.6, 14.1Hz), 4.72 (d, 1H, J =
2
1
3
1
5.7Hz), 4.04 (brs, 1H); C NMR (CDCl , 100MHz) δ 174.8,
3
ACS Paragon Plus Environment

Page 7 of 10
The Journal of Organic Chemistry
+
1
1
41.4, 134.2, 133.7, 132.0, 129.0, 128.6, 128.1, 128.0, 127.4,
27.0, 124.1, 122.3, 121.4, 116.5, 111.6, 75.1, 55.1, 44.2; ESI-
55.3, 26.5, 21.1; ESI-HRMS(m/z): [M+H] calcd.
C H N O , 335.1508, found 335.1503.
for
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
1
9
19
4
2
+
HRMS(m/z): [M+H] calcd. for C H Br N O , 552.9875,
3-((4-(4-Bromophenyl)-1H-1,2,3-triazol-1-yl)methyl)-3-
24
19
2
4
2
found 552.9874.
-Benzyl-5-bromo-3-hydroxy-3-((4-(4-
methoxyphenyl)-1H-1,2,3-triazol-1-yl)methyl)indolin-
-one [6f(iii)]
White solid; mp 206-208 C; Yield: 0.35g, 69%; H NMR
CDCl , 400 MHz) δ 7.78-7.73 (m, 2H), 7.37-7.32 (m, 2H),
hydroxy-1,5-dimethylindolin-2-one [6h(ii)]
Yellow solid; mp 208-210 C; Yield: 0.30g, 72%; H NMR
◦
1
1
(CDCl , 400 MHz) δ 8.01 (s, 1H), 7.73-7.70 (m, 2H), 7.57-
3
2
7.54 (m, 2H), 7.17-7.14 (m, 1H), 6.74-6.68 (m, 2H), 4.78 (d,
◦
1
1H, J = 14.2Hz), 4.74 (d, 1H, J = 14.2Hz), 4.00 (brs, 1H), 3.17
1
3
(
(s, 3H), 2.27 (s, 3H); C NMR (CDCl , 100MHz) δ 175.2,
3
3
7.25-7.23 (m, 3H), 7.17-7.15 (m, 2H), 6.98 (d, 2H, J =
146.6, 140.6, 133.5, 132.0, 131.0, 129.4, 127.3, 126.7, 125.3, 122.1,
121.6, 108.7, 75.2, 55.4, 26.5, 21.1; ESI-HRMS(m/z): [M+H]
+
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
8
4
.7Hz), 6.56 (d, 1H, J = 8.4Hz), 4.97 (d, 1H, J = 15.7Hz),
.85 (q, 2H, J = 14.1, 15.6Hz), 4.74 (d, 1H, J = 15.7Hz), 3.87
calcd. for C H BrN O , 413.0613, found 413.0607.
1
9
18
4
2
1
3
(
s, 3H); C NMR (DMSO-d , 100MHz) δ 176.1, 160.3, 147.1,
3-Hydroxy-3-((4-(4-methoxyphenyl)-1H-1,2,3-triazol-1-
6
1
1
43.0, 136.6, 133.7, 131.9, 129.8, 128.9, 128.6, 128.2, 127.8,
yl)methyl)-1,5-dimethylindolin-2-one [6h(iii)]
◦
1
24.3, 122.9, 115.6, 115.6, 112.7, 75.8, 56.4, 55.1, 44.1; ESI-
Brownish solid; mp 204-206 C; Yield: 0.27g, 74%; H NMR
+
HRMS(m/z): [M+H] calcd. for C H BrN O , 505.0875,
(CDCl , 400 MHz) δ 7.89 (s, 1H), 7.79-7.77 (m, 2H), 7.32-
25
22
4
3
3
found 505.0870.
3-Hydroxy-5-methoxy-1-methyl-3-((4-phenyl-1H-1,2,3-
7.31 (m, 1H), 7.15 (d, 1H, J = 7.8Hz), 6.99-6.97 (m, 2H), 6.73
(d, 1H, J = 7.9Hz), 4.78-4.74 (m, 2H), 3.87 (s, 3H), 3.19 (s,
1
3
triazol-1-yl)methyl) indolin-2-one [6g(i)]
Yellow solid; mp 198-200 C; Yield: 0.27g, 78%; H NMR
3H), 2.27 (s, 3H); C NMR (CDCl , 100MHz) δ 159.7, 140.7,
3
◦
1
133.5, 131.0, 127.1, 126.7, 125.4, 124.1, 123.1, 120.6, 115.9, 114.3,
108.7, 75.3, 55.4, 31.6, 26.5, 21.1; ESI-HRMS(m/z): [M+H]
+
(CDCl , 400 MHz) δ 8.03 (s, 1H), 7.86-7.84 (m, 2H), 7.47-
3
7.43 (m, 2H), 7.38-7.35 (m, 1H), 6.87 (dd, 1H, J = 2.6,Hz),
6.75 (d, 1H, J = 8.5Hz), 6.36 (d, 1H, J = 2.5Hz), 4.82(d, 1H, J
= 14.2Hz), 4.73 (d, 1H, J = 14.2Hz), 3.97 (brs, 1H), 3.67 (s,
calcd. for C H N O , 365.1614, found 365.1608.
20
21
4
3
1-Benzyl-3-hydroxy-5-methyl-3-((4-phenyl-1H-1,2,3-
triazol-1-yl)methyl) indolin-2-one [6i(i)]
1
3
◦
1
3H), 3.19 (s, 3H); C NMR (CDCl , 100MHz) δ 174.9, 156.6,
White solid; mp 148-151 C; Yield: 0.32g, 78%; H NMR
3
136.2, 130.3, 128.9, 128.3, 127.7, 125.8, 121.5, 115.8, 111.1, 109.6,
(CDCl , 400 MHz) δ 7.93 (d, 1H, J = 2.8Hz), 7.80 (d, 2H, J =
3
+
75.5, 55.7, 55.4, 26.6; ESI-HRMS(m/z): [M+H] calcd. for
7.9Hz), 7.44-7.38 (m, 2H), 7.37-7.31 (m, 1H), 7.21-7.09 (m,
5H), 7.07-7.00 (m, 1H), 6.80 (s, 1H), 6.57 (d, 1H, J = 8.0Hz),
4.96-4.82 (m, 3H), 4.70 (d, 1H, J = 15.6Hz), 3.12 (brs, 1H),
C H N O , 351.1457, found 351.1445.
1
9
19
4
3
3-((4-(4-Bromophenyl)-1H-1,2,3-triazol-1-yl)methyl)-3-
1
3
hydroxy-5-methoxy -1-methylindolin-2-one [6g(ii)]
2.24 (s, 3H); C NMR (CDCl , 100MHz) δ 175.6, 147.7,
3
◦
1
White solid; mp 204-206 C; Yield: 0.31g, 73%; H NMR
139.9, 134.8, 133.5, 130.9, 130.3, 128.9, 128.8, 128.7, 128.2,
127.8, 127.0, 126.8, 125.8, 125.5, 121.4, 75.5, 55.2, 44.1, 21.0;
(CDCl , 400 MHz) δ 8.05 (s, 1H), 7.70 (d, 2H, J = 8.4Hz),
3
+
7.54 (d, 2H, J = 8.4Hz), 6.86 (dd, 1H, J = 2.4Hz), 6.74 (d,
1H, J = 8.5Hz), 6.39 (d, 1H, J = 2.4Hz), 4.78 (d, 1H, J =
14.2Hz), 4.73 (d, 1H, J = 14.2Hz), 4.33 (brs, 1H), 3.67 (s, 3H),
ESI-HRMS(m/z): [M+H] calcd. for C H N O , 411.1821,
25
23
4
2
found 411.1813.
1-Benzyl-3-((4-(4-bromophenyl)-1H-1,2,3-triazol-1-
1
3
3.16 (s, 3H); C NMR (CDCl , 100MHz) δ 174.9, 156.6, 146.7,
yl)methyl)-3-hydroxy-5-methylindolin-2-one [6i(ii)]
3
◦
1
136.1, 132.0, 129.3, 127.7, 127.3, 122.2, 121.6, 115.7, 111.2, 109.6,
White solid; mp 208-210 C; Yield: 0.36g, 73%; H NMR
+
75.4, 55.8, 55.5, 26.6; ESI-HRMS(m/z): [M+H] calcd. for
(CDCl , 400 MHz) δ 7.93 (s, 1H), 7.66 (d, 2H, J = 8.5Hz),
3
C H BrN O , 429.0562, found 429.0551.
7.55-7.53 (m, 2H), 7.23-7.14 (m, 5H), 7.03 (d, 1H, J = 8.8Hz),
6.80 (s, 1H), 6.59 (d, 1H, J = 8.0Hz), 4.96 (d, 1H, J =
15.6Hz), 4.86-4.85 (m, 2H), 4.71 (d, 1H, J = 15.6Hz), 2.25 (s,
1
9
18
4
3
3-Hydroxy-5-methoxy-3-((4-(4-methoxyphenyl)-1H-
1,2,3-triazol-1-yl)methyl)-1-methylindolin-2-one
[6g(iii)]
1
3
3H); C NMR (CDCl , 100MHz) δ 175.5, 146.7, 139.9, 134.8,
3
◦
1
Yellow solid; mp 168-170 C; Yield: 0.28g, 75%; H NMR
133.6, 132.0, 131.0, 129.3, 128.9, 127.9, 127.3, 127.0, 126.7,
125.4, 122.1, 121.5, 109.8, 75.3, 55.3, 44.1, 21.0; ESI-
(CDCl , 400 MHz) δ 7.96 (s, 1H), 7.76-7.74 (m, 2H), 6.97-
3
+
6.94 (m, 2H), 6.84 (dd, 1H, J = 2.5, 2.6Hz), 6.72 (d, 1H, J =
8.5Hz), 6.36 (d, 1H, J = 2.5Hz), 4.80 (d, 1H, J = 14.2Hz),
4.70 (d, 1H, J = 14.2Hz), 4.48 (brs, 1H), 3.86 (s, 3H), 3.68 (s,
HRMS(m/z): [M+H] calcd. for C H BrN O , 489.0926,
25
22
4
2
found 489.0916.
1-Benzyl-3-hydroxy-3-((4-(4-methoxyphenyl)-1H-1,2,3-
1
3
3H), 3.16 (s, 3H); C NMR (CDCl , 100MHz) δ 175.2, 159.6,
triazol-1-yl)methyl)-5-methylindolin-2-one [6i(iii)]
3
◦
1
156.6, 147.6, 136.1, 127.9, 127.1, 123.0, 120.8, 115.7, 114.2, 111.1,
Brown solid; mp 228-230 C; Yield: 0.33g, 75%; H NMR
+
109.5, 75.6, 55.7, 55.4, 55.3, 26.6; ESI-HRMS(m/z): [M+H]
(CDCl , 400 MHz) δ 7.83 (s, 1H), 7.74 (d, 2H, J = 8.8Hz),
3
calcd. for C H N O , 381.1563, found 381.1550.
7.32-7.29 (m, 1H), 7.25-7.16 (m, 5H), 7.03-6.96 (m, 2H),
6.79 (s, 1H), 6.58 (d, 1H, J = 8.0Hz), 4.97 (d, 1H, J = 15.6Hz),
20
21
4
4
3-Hydroxy-1,5-dimethyl-3-((4-phenyl-1H-1,2,3-triazol-
1-yl)methyl) indolin-2-one [6h(i)]
Yellow solid; mp 196-198 C; Yield: 0.25g, 75%; H NMR
4.85 (q, 2H, J = 14.0Hz), 4.74 (d, 1H, J = 15.7Hz), 3.87 (s,
◦
1
13
3H), 2.24 (s, 3H); C NMR (CDCl , 100MHz) δ 175.4, 147.6,
3
(CDCl , 400 MHz) δ 8.02 (d, 1H, J = 3.1Hz), 7.86-7.84 (m,
139.9, 134.8, 133.5, 131.0, 128.9, 128.9, 127.8, 127.2, 127.1, 126.7,
125.4, 123.1, 120.5, 114.2, 109.8, 75.4, 55.4, 55.2, 44.1, 29.7;
3
2H), 7.46-7.42 (m, 2H), 7.38-7.33 (m, 1H), 7.14-7.12 (m,
1H), 6.72 (d, 1H, J = 8.0Hz), 6.66-6.64 (m, 1H), 4.79 (d,
+
ESI-HRMS(m/z): [M+H] calcd. for C H N O , 441.1927,
26
25
4
3
1
3
H, J = 2.8Hz), 4.74 (d, 1H, J = 13.0Hz), 3.17 (s, 3H), 2.25 (s,
found 441.1916.
1
3
H); C NMR (CDCl , 100MHz) δ 175.4, 147.6, 140.6, 133.4,
Ethyl
1-((3-hydroxy-1-methyl-2-oxoindolin-3-
3
1
30.9, 130.5, 128.8, 128.2, 126.8, 125.8, 125.4, 121.5, 108.6, 75.4,
yl)methyl)-1H-1,2,3-triazole-4-carboxylate (7a)
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 8 of 10
◦
1
Yellow solid; mp 200-202 C; Yield: 0.25g, 78%; H NMR
127.1, 116.6, 111.6, 74.9, 61.5, 55.2, 44.2, 14.3; ESI-
+
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
(
CDCl , 400 MHz) δ 8.40 (s, 1H), 7.38-7.34 (m, 1H), 7.05-
HRMS(m/z): [M+H] calcd. for C H BrN O , 471.0668,
21 20 4 4
3
7
.02 (m, 1H), 6.86 (d, 1H, J = 7.8Hz), 6.69 (d, 1H, J =
found 471.0664.
Ethyl
oxoindolin-3-yl)methyl)-1H-1,2,3-triazole-4-
carboxylate (7g)
7.3Hz), 4.80 (d, 1H, J = 14.1Hz), 4.75 (d, 2H, J = 14.1Hz),
1-((3-hydroxy-5-methoxy-1-methyl-2-
4
.43 (q, 2H, J = 7.1Hz), 4.37 (brs, 1H), 3.20 (s, 3H), 1.42 (t,
1
3
3
H, J = 7.2, 14.3Hz); C NMR (CDCl , 100MHz) δ 175.2,
3
◦
1
1
60.8, 142.9, 140.2, 130.9, 129.4, 126.4, 124.5, 123.9, 109.1,
Yellow solid; mp 176-178 C; Yield: 0.26g, 76%; H NMR
+
74.8, 61.5, 55.4, 26.6, 14.3; ESI-HRMS(m/z): [M+H] calcd.
(CDCl , 400 MHz) δ 8.39 (s, 1H), 6.86 (dd, 1H, J = 2.5,
3
for C H N O , 317.1250, found 317.1238.
Ethyl
yl)methyl)-1H-1,2,3-triazole-4-carboxylate (7b)
6.0Hz), 6.76 (d, 1H, J = 8.6Hz), 6.36 (d, 1H, J = 2.5Hz), 4.80
(d, 1H, J = 14.2Hz), 4.75 (d, 1H, J = 14.1Hz), 4.42 (q, 2H, J =
7.1, 14.2Hz), 4.36 (brs, 1H), 3.70 (s, 3H), 3.18 (s, 3H), 1.42 (t,
3H, J = 3.4, 7.1Hz); C NMR (CDCl , 100MHz) δ 175.0,
160.7, 156.7, 140.2, 136.0, 129.4, 127.6, 115.6, 111.4, 109.7, 75.2,
1
5
17
4
4
1-((1-benzyl-3-hydroxy-2-oxoindolin-3-
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
◦
1
13
Yellow solid; mp 138-140 C; Yield: 0.28g, 72%; H NMR
CDCl , 400 MHz) δ 8.35 (s, 1H), 7.34-7.28 (m, 3H), 7.28-
3
(
3
+
7.22 (m, 3H), 7.04-7.00 (m, 1H), 6.77-6.73 (m, 2H), 4.98 (d,
61.4, 55.8, 55.5, 26.6, 14.3; ESI-HRMS(m/z): [M+H] calcd.
1
H, J = 15.6Hz), 4.85-4.78 (m, 3H), 4.44 (q, 2H, J = 7.2Hz),
for C H N O , 347.1355, found 347.1354.
1
6
19
4
5
1
3
3.69 (brs, 1H), 1.43 (t, 3H, J = 7.1, 14.3Hz); C NMR (CDCl3,
100MHz) δ 175.0, 160.7, 142.2, 140.3, 134.7, 131.0, 129.3, 129.0,
128.0, 127.2, 126.2, 124.6, 123.9, 110.1, 74.9, 61.5, 55.5, 44.2,
14.3; ESI-HRMS(m/z): [M+H] calcd. for C H N O ,
393.1563, found 393.1550.
Ethyl 1-((5-chloro-3-hydroxy-1-methyl-2-oxoindolin-3-
yl)methyl)-1H-1,2,3-triazole-4-carboxylate (7c)
White solid; mp 208-210 C; Yield: 0.27g, 76%; H NMR
(CDCl , 400 MHz) δ 8.34 (s, 1H), 7.36-7.33 (m, 1H), 6.88 (d,
1H, J = 2.1Hz), 6.79 (d, 1H, J = 8.4Hz), 4.79 (s, 2H), 4.43 (q,
2H, J = 7.1Hz), 3.19 (s, 3H), 1.43 (t, 3H, J = 7.2, 14.3Hz);
NMR (DMSO-d , 100MHz) δ 179.7, 165.4, 147.4, 143.5, 135.6,
135.1, 134.9, 131.6, 129.7, 115.6, 79.3, 65.8, 59.2, 31.4, 19.3; ESI-
HRMS(m/z): [M+H] calcd. for C H ClN O , 351.0860,
found 351.0847.
Ethyl 1-((1-benzyl-5-chloro-3-hydroxy-2-oxoindolin-3-
yl)methyl)-1H-1,2,3-triazole-4-carboxylate (7d)
Yellow solid; mp 120-122 C; Yield: 0.29g, 68%; H NMR
(CDCl , 400 MHz) δ 8.30 (s, 1H), 7.33-7.31 (m, 3H), 7.24-
7.17 (m, 3H), 6.92 (d, 1H, J = 2.0Hz), 6.67-6.62 (m, 1H),
4.94 (d, 1H, J = 15.6Hz), 4.85-4.75 (m, 3H), 4.44 (q, 2H, J =
7.1, 14.2Hz), 4.06 (brs, 1H), 1.44 (t, 3H, J = 2.9, 7.1Hz);
NMR (CDCl , 100MHz) δ 174.7, 160.6, 140.7, 140.3, 134.2,
130.9, 129.4, 129.3, 129.1, 128.2, 128.0, 127.1, 125.2, 124.1, 74.9,
61.5, 55.2, 44.3, 14.3; ESI-HRMS(m/z): [M+H] calcd. for
C H ClN O , 427.1173, found 427.1163.
Ethyl 1-((5-bromo-3-hydroxy-1-methyl-2-oxoindolin-3-
yl)methyl)-1H-1,2,3-triazole-4-carboxylate (7e)
White solid; mp 196-198 C; Yield: 0.29g, 73%; H NMR
(CDCl , 400 MHz) δ 8.32 (s, 1H), 7.50-7.48 (m, 1H), 7.06-
7.03 (m, 1H), 6.74-6.70 (m, 1H), 4.80 (d, 2H, J = 13.9Hz),
4.42 (q, 2H, J = 7.1, 14.2Hz), 4.23 (brs, 1H), 3.18 (s, 3H), 1.43
(t, 3H, J = 2.6, 7.1Hz); C NMR (CDCl , 100MHz) δ 174.6,
160.6, 142.0, 140.2, 133.8, 129.4, 128.4, 127.8, 116.5, 110.5, 74.8,
61.5, 55.2, 26.7, 14.3; ESI-HRMS(m/z): [M+H] calcd. for
Ethyl
1-((3-hydroxy-1,5-dimethyl-2-oxoindolin-3-
yl)methyl)-1H-1,2,3-triazole-4-carboxylate (7h)
White solid; mp 168-170 C; Yield: 0.24g, 74%; H NMR
◦
1
+
(CDCl , 400 MHz) δ 8.37 (s, 1H), 7.16 (d, 1H, J = 7.9Hz),
21
21
4
4
3
6.75 (d, 1H, J = 8.0Hz), 6.63 (d, 1H, J = 10.8Hz), 4.77 (s,
2H), 4.45 (q, 2H, J = 7.2, 14.3Hz), 3.72 (brs, 1H), 3.20 (s,
3H), 2.28 (s, 3H), 1.44 (t, 3H, J = 4.6, 8.6Hz); C NMR
1
3
◦
1
(CDCl , 100MHz) δ 174.9, 151.8, 140.5, 133.7, 131.2, 126.3,
3
125.2, 124.1, 115.9, 108.8, 74.9, 61.4, 55.5, 29.7, 26.6, 14.3;
ESI-HRMS(m/z): [M+H] calcd. for C H N O , 331.1406,
found 331.1402.
Ethyl 1-((1-benzyl-3-hydroxy-5-methyl-2-oxoindolin-3-
yl)methyl)-1H-1,2,3-triazole-4-carboxylate (7i)
Brown solid; mp 96-98 C; Yield: 0.28g, 69%; H NMR
3
+
1
6
19
4
4
1
3
C
6
+
◦
1
1
5
16
4
4
(CDCl , 400 MHz) δ 8.33 (s, 1H), 7.33-7.29 (m, 2H), 7.27-
3
7.18 (m, 3H), 7.03 (d, 1H, J = 7.8Hz), 6.65-6.61 (m, 2H),
4.93 (d, 1H, J = 15.6Hz), 4.83 (s, 2H), 4.75 (d, 1H, J =
15.6Hz), 4.42 (q, 2H, J = 7.0, 14.1Hz), 4.19 (brs, 1H), 2.24 (s,
3H), 1.42 (t, 3H, J = 7.1, 13.2Hz);
100MHz) δ 175.2, 160.7, 140.2, 139.7, 134.8, 133.7, 131.1, 129.4,
129.0, 127.9, 127.2, 126.4, 125.3, 109.9, 75.1, 61.4, 55.4, 44.1,
21.0, 14.3; ESI-HRMS(m/z): [M+H] calcd. for C H N O ,
407.1719, found 407.1712.
◦
1
1
3
C NMR (CDCl3,
3
1
3
+
C
22
23
4
4
3
+
ACKNOWLEDGMENT
21
20
4
4
Research funding (Award No. SR/S1/OCꢀ29/2011) from the
department of science and technology (DST), Government of
India is gratefully acknowledged.
◦
1
ASSOCIATED CONTENT
3
The Supporting Information is available free of charge on the
1
ACS Publications website. A copy of scanned spectra ( H
1
3
13
3
NMR, C NMR and HRMS) can be found in the online ver-
sion (file type, i.e., MS Word).
+
C H BrN O , 395.0355, found 395.0346.
Ethyl 1-((1-benzyl-5-bromo-3-hydroxy-2-oxoindolin-3-
yl)methyl)-1H-1,2,3-triazole-4-carboxylate (7f)
Yellow solid; mp 124-126 C; Yield: 0.31g, 66%; H NMR
(CDCl , 400 MHz) δ 8.30 (s, 1H), 7.38-7.29 (m, 4H), 7.18-
7.16 (m, 2H), 7.08 (d, 1H, J = 1.9Hz), 6.60 (d, 1H, J = 8.4Hz),
4.92 (d, 1H, J = 15.7Hz), 4.85 (s, 2H), 4.75 (d, 1H, J =
AUTHOR INFORMATION
1
5
16
4
4
Corresponding Author
◦
1
* ravindra.rawal@gmail.com, vn74nr@yahoo.com,
3
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1
60.6, 141.2, 140.3, 134.2, 133.7, 129.3, 129.1, 128.5, 128.2, 127.9,
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