Facile synthesis of 4,5-disubstituted 2h-1,2,3-triazoles by catalyst-free cycloaddition between substituted vinyl sulfones and sodium azide under ambient conditions

Article abstract of DOI:10.1002/cjoc.201200998

A highly efficient method for readily preparing 4,5-disubstituted 2H-1,2,3-triazoles was found. Under ambient conditions, a catalyst free cycloaddition between substituted vinyl sulfones and sodium azide could be completed in a very short time. In this cycloaddition process, sulfonyl group acts as a leaving group, while its ester group was retained. A highly efficient method for readily preparing 4,5-disubstituted 2H-1,2,3-triazoles was found. Under ambient conditions, a catalyst free cycloaddition between substituted vinyl sulfones and sodium azide could be completed in a very short time. In this cycloaddition process, sulfonyl group acts as a leaving group, while its ester group was retained. Copyright

Full text of DOI:10.1002/cjoc.201200998

FULL PAPER
DOI: 10.1002/cjoc.201200998
Facile Synthesis of 4,5-Disubstituted 2H-1,2,3-Triazoles by
Catalyst-free Cycloaddition between Substituted Vinyl Sul-
fones and Sodium Azide under Ambient Conditions†
Yang, Jinjin(杨金金)
Yin, Wei(殷伟)
Liu, Renhua(刘仁华)
Chu, Changhu*(褚长虎)
School of Pharmacy, Shanghai Key Laboratory of New Drug Design, East China University of Science and Tech-
nology, 130 Meilong Road, Shanghai 200237, China
A highly efficient method for readily preparing 4,5-disubstituted 2H-1,2,3-triazoles was found. Under ambient
conditions, a catalyst free cycloaddition between substituted vinyl sulfones and sodium azide could be completed in
a very short time. In this cycloaddition process, sulfonyl group acts as a leaving group, while its ester group was re-
tained.
Keywords vinyl sulfone, sodium azide, cycloaddition, 1,2,3-triazole, catalyst free
Introduction
could not be prepared directly by catalytic cycloaddition.
Recently, a few of methods for the synthesis of
1,2,3-triazoles are reported, including Pd catalyzed
cycloaddition between sodium azide and alkynes with
an electron withdrawing substituent, the reaction of so-
dium azide with nitroalkenes, the rearrangement of
propargyl azides and other strategies which requires
deprotection steps and the employment of more elabo-
rated azides.[7] It is noticeable that most of these proc-
esses have drawbacks, such as high temperature, time
consuming, low yield and requirement of transient
metal-phosphine complex as catalyst.
Recently, we prepared a type of substituted vinyl
sulfones through the Ti(Oi-Pr)4 mediated Knoevenagel
condensation between benzothiazol-2-yl sulfones 1 (BT
sulfone, Julia reagent) and aldehydes with good yield
and exclusively E isomers.[8] With the substituted vinyl
sulfone, we explored sodium azide as a nucleophile re-
agent to react with these substituted vinyl sulfones in
DMSO for the preparation of sulfonyl azides by a
1,4-Michael addition. However, no sulfonyl azides are
formed, instead, disubstituted 2H-1,2,3-triazoles 2 are
obtained with excellent yield at room temperature
within a few minutes (Scheme 1). This is an unexpected
result, and it should be an alternative access for readily
and efficiently obtaining 2H-1,2,3-triazoles. For the re-
action of allenyl esters with sodium azide, only azide
addition product was obtained, and no cycloaddition
product was observed.[9] Herein, we would like to de-
scribe our findings on this new and interesting reaction.
1,2,3-Triazoles are an important type of heterocyclic
compounds due to their broad spectrum biological ac-
tivities. They are widely employed in pharmaceutical
and agrochemical fields. Other industrial application
related to 1,2,3-triazole compounds have also been de-
veloped, such as dyes, corrosive inhibitors and photo-
stabilizers.[1] The conventional route to 1,2,3-triazoles is
the Huisgen 1,3-dipolar cycloaddition of alkynes with
organic azides. Since Sharpless[2] developed
Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) to
achieve 1,2,3-triazoles with great efficiency and selec-
tivity, this reaction has become one of the most effective
methods for preparing variety of 1,2,3-triazoles con-
taining compounds, and it has been widely applied as a
powerful tool in related research fields, such as biocon-
jugation, material science and drug discovery, and their
related applications have been reviewed.[3] Except Cu(I)
catalyst, other organic and inorganic catalyst are also
used to promote this reaction.[4] On the other hand, for
biological study requirement, transient metal free
1,3-dipolar cycloaddition between azides and strained
alkynes such as cyclooctynes to form 1,2,3-triazoles at
lower temperature without using any toxic catalyst was
reported.[5] However, multiple steps reactions are usu-
ally required to prepare such kind of strained alkynes. In
most of above mentioned cases, only organic azides
could be used as substrates in this reaction, and inex-
pensive inorganic azides are not good substrate. Thus
1,2,3-triazoles, which also have a wide range of uses
due to organic synthesis and its biological activities,[6]
*
E-mail: chuch@ecust.edu.cn
Received October 13, 2012; accepted November 19, 2012; published online December 13, 2012.
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/cjoc.201200998 or from the author.
Dedicated to the 60th Anniversary of East China University of Science and Technology.
†
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© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2012, 30, 2786—2790

Facile Synthesis of 4,5-Disubstituted 2H-1,2,3-Triazoles by Catalyst-free Cycloaddition
Scheme 1 Cycloaddition between substituted vinyl sulfones and
sodium azide to afford 4,5-disubstituted 2H-1,2,3-triazoles
Table 2 Reaction of substituted vinyl sulfones with sodium
azide
Entry
1
R
Solvent Reaction time Yielda/%
H
R
N
O
S
NaN3
DMSO
N
N
S
N
phenyl (a)
DMSO
5 min
98
O
O
r.t., 5 min 2 h
—
2,4-dimethoxyl
phenyl (b)
O
R
O
1
2
3
DMSO
2 h
95
O
2
2,3-dimethoxyl
phenyl (c)
DMSO
DMSO
20 min
97
Results and Discussion
This is an efficient and rapid access for easily pre-
paring 4,5-disubstituted 1,2,3-triazoles without using
any catalyst, in which commercial solvents such as
DMSO, DMF, ethanol and methanol could be used di-
rectly without any preliminary purification (Table 1).
Further more, reaction time is also very short and no
critical reaction condition is required. In most of these
cases, reaction could be completed in 2 h. However,
when other solvents, such as water, chloroform and di-
chloromethane (Table 1), were utilized in this reaction,
no reaction was observed, which may be attributed to
insolubility of vinyl sulfones in water and sodium azide
in chloroform and dichloromethane respectively. Then
the reaction was carried out in DMSO. Under the same
reaction conditions, the scope of this reaction was tested:
all these substituted vinyl sulfones could react readily
with sodium azide to afford 4,5-disubstituted 2H-1,2,3-
triazoles with good to excellent yields (Table 2).
4
5
6
7
8
9
4-chloro phenyl (d)
5 min
10 min
5 min
10 min
1.5 h
98
94
96
95
95
98
98
96
90
95
95
96
2,4-dichloro phenyl (e) DMSO
4-methoxy phenyl (f)
4-bromo phenyl (g)
2-furyl (h)
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
4-methyl phenyl (i)
5 min
5 min
5 min
2 h
10 1-naphthyl (j)
11 4-fluoro phenyl (k)
12 3-bromo phenyl (l)
13 2-naphthyl (m)
14 2-methyl phenyl (n)
15 heptyl (o)
5 min
10 min
40 min
a Reaction conditions: sulfone ( 0.3 mmol), NaN3 (21 mg, 0.32
mmol) in 3 mL DMSO, isolated yield.
Scheme 2 Possible reaction pathway to form 2H-1,2,3-triazole
by a cycloaddition between substituted vinyl sulfones and sodium
azide
Table 1 Solvent effect on the reaction of substituted vinyl sul-
fones with sodium azide
R
Solvent
DMSO
DMF
Reaction time
5 min
Conversiona/%
phenyl (a)
phenyl (a)
phenyl (a)
phenyl (a)
phenyl (a)
phenyl (a)
phenyl (a)
100
100
NR
100
100
NR
NR
H
N
5 min
N
NaN3
O
S
O
N
S
N
S
N
S
O
H2O
overnight
4.5 h
DMSO, r.t.
O
O
O
O
O
MeOH
EtOH
O
2 h
H
N
N
β
-elimination
CHCl3
CH2Cl2
overnight
overnight
N
HN
O
O
N
N
O
O
a Reaction conditions: sulfone (39 mg, 0.1 mmol), NaN3 (7 mg,
0.105 mmol) in 1 mL solvent, and the reaction was detected by
TLC or GC, NR (no reaction).
N
S
H+
N
S
S ONa
- SO2
The possible reaction pathway could be proposed as
follows (Scheme 2): a [3＋2] cycloaddition between
vinyl sulfone and azide anion forms a 1,2,3-triazole in-
termediate substituted by sulfonyl, ester and phenyl
groups, which would then undergo a β-elimination to
afford 4,5-substituted 2H-1,2,3-triazole, and the by-
product may be water soluble sodium benzo[d]thiazole-
2-sulfinate. This was confirmed by a reaction in NMR
tube (1H NMR, DMSO-d6), a group of peaks related to
2-substituted benzo[d]thiazole protons appeared after
addition of sodium azide to vinyl sulfone in DMSO-d6,
while the olefine proton in substrate disappeared.
After the reaction was quenched by water, only
4,5-substituted 1,2,3-triazole was extracted out. Further
more, when the aqueous layer was acidified with
aqueous HCl and extracted with ethyl acetate,
benzo[d]thiazole could be detected by GC-Mass. In this
case, sulfonyl group acts as a leaving group, while its
ester group is retained.
However, under this reaction condition, organic
azide does not react with these substituted vinyl sul-
fones at all, which may be attributed to that the vinyl
sulfone acts as an electronic acceptor while the sodium
azide as an electronic donor in the reaction. The azide
Chin. J. Chem. 2012, 30, 2786—2790
© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Yang et al.
FULL PAPER
anion in sodium azide obviously possesses the stronger
nucleophilic property than that of organic azide, thus
azide anion may react with vinyl sulfone by an addition
process firstly, then cyclization and elimination to
achieve corresponding 1,2,3-triazole subsequently.
While organic azide could not react with vinyl sulfone
firstly due to its weak nucleophilic attach ability.
MHz, CDCl3) δ: 13.12 (s, 1H), 7.96—7.94 (m, 1H),
6.63 (dd, J＝2.4, 8.8 Hz, 1H), 6.56—6.64 (m, 2H), 5.25
—5.32 (m, 1H), 3.88 (s, 6H), 1.37 (d, J＝6.0 Hz, 6H);
13C NMR (100 MHz, CDCl3) δ: 162.4, 161.4, 157.9,
132.8, 104.8, 98.6, 68.9, 55.7, 55.5, 21.8; HRMS (ESI)
calcd for C14H17N3O4 [M ＋ Na] ＋ 314.1117, found
314.1133.
Isopropyl
5-(2,3-dimethoxyphenyl)-2H-1,2,3-tria-
zole-4-carboxylate (2c): Prepared from 1c (134 mg, 0.3
mmol) and NaN3 (0.32 mmol, 21 mg). Colourless oil;
yield 85 mg, 97%; V(petroleum ether)∶V(ethyl acetate)
＝1∶1, Rf＝0.3; 1H NMR (400 MHz, CDCl3) δ: 7.36 (s,
1H), 7.17 (t, J＝8.0 Hz, 1H), 7.04 (d, J＝8.4 Hz, 1H),
5.24—5.30 (m, 1H), 3.92 (s, 3 H), 3.70 (s, 3H), 1.33 (d,
J＝6.4 Hz, 6H); 13C NMR (100 MHz, CDCl3) δ: 160.9,
Conclusions
In summary, a novel access for readily and
efficiently preparation of 4,5-disubstituted 2H-1,2,3-
triazoles was found. Without using any catalyst,
disubstituted vinyl sulfones could react with sodium
azide quickly under ambient conditions.
152.6, 146.7, 124.2, 123.1, 114.0, 69.2, 61.2, 55.9, 21.7;
HRMS (ESI) calcd for C14H17N3O4 [M ＋ Na]
＋
Experimental
1H NMR and 13C NMR spectra were recorded on a
Bruker AV400. Chemical shifts (δ) are referenced to the
solvent residual peak: proton (chloroform δ 7.26), car-
bon (chloroform δ 77.0) and TMS peak as an internal
standard. High resolution mass spectra (HRMS) were
performed using a Bruker Daltronics MicroTof. TLC
analyses were performed on commercial aluminum
sheets bearing 0.25 mm layer of silica gel. 200—300
mesh silica gel was used for column chromatography.
All chemicals were of reagent grade quality obtained
from commercial sources and used without further puri-
fication unless otherwise noted.
314.1117, found 314.1135.
Isopropyl 5-(4-chlorophenyl)-2H-1,2,3-triazole-4-
carboxylate (2d): Prepared from 1d (126 mg, 0.3 mmol)
and NaN3 (0.32 mmol, 21 mg). White solid; yield 78 mg,
98%; m.p. 132—133 ℃; V(petroleum ether)∶V(ethyl
acetate)＝2∶1, Rf＝0.3; 1H NMR (400 MHz, CDCl3) δ:
7.83 (d, J＝8.4 Hz, 2H), 7.44 (d, J＝8.4 Hz, 2H), 5.28
—5.34 (m, 1H), 1.36 (d, J＝6.0 Hz, 6H); 13C NMR (100
MHz, CDCl3) δ: 160.9, 136.0, 130.9, 128.7, 70.0, 21.5;
TOF-MS calcd for C12H12ClN3O2 [M]＋ 265.06168,
found 265.0616.
Isopropyl 5-(2,4-dichlorophenyl)-2H-1,2,3-triazole-
4-carboxylate (2e): Prepared from 1e (137 mg, 0.3
mmol) and NaN3 (0.32 mmol, 21 mg). White solid;
yield 84 mg, 94%; m.p. 104—105 ℃; V(petroleum
General procedure for the synthesis of 4,5-disub-
stituted 2H-1,2,3-triazoles 2
1
ether)∶V(ethyl acetate)＝2∶1, Rf＝0.3; H NMR (400
Substituted vinyl sulfone 1 (0.30 mmol) and NaN3
(21 mg, 0.32 mmol, 1.06 equiv.) were added into
DMSO (3 mL) in turn, and the mixture was stirred at
room temperature. The reaction was detected by TLC.
After substituted vinyl sulfone 1 was consumed out, 15
mL of H2O was added and extracted with EtOAc (15
mL×3). The combined organic layer was dried over
anhydrous Na2SO4. Removal of all solvent left a residue
which was passed through a flash silica gel column
[V(petroleum ether)∶V(EtOAc)＝4∶1, as eluent] to
afford product 4,5-substituted 1H-1,2,3-triazoles 2.
Isopropyl 5-phenyl-2H-1,2,3-triazole-4-carboxylate
(2a): Prepared from 1a (116 mg, 0.3 mmol) and NaN3
(0.32 mmol, 21 mg). White solid; yield 68 mg, 98%;
m.p. 68—69 ℃; V(petroleum ether)∶V(ethyl acetate)
＝2∶1, Rf＝0.3; 1H NMR (400 MHz, CDCl3) δ: 7.84—
7.82 (m, 2H), 7.46 (t, J＝3.2 Hz, 3H), 5.26—5.32 (m,
1H), 1.33 (d, J＝6.4 Hz, 6H); 13C NMR (100 MHz,
CDCl3) δ: 160.7, 129.6, 129.3, 128.3, 69.7, 21.7; HRMS
(ESI) calcd for C12H13N3O2 [M]＋ 231.1008, found
231.1007.
MHz, CDCl3) δ: 7.53 (d, J＝2.0 Hz, 1H), 7.42—7.34 (m,
2H), 5.19—5.25 (m, 1H), 1.24 (d, J＝6.4 Hz, 6H); 13C
NMR (100 MHz, CDCl3) δ: 160.4, 136.1, 135.0, 132.4,
129.4, 127.0, 69.7, 21.1; HRMS (ESI) calcd for
C12H11Cl2N3O2 [M＋Na]＋ 322.0126, found 322.0144.
Isopropyl 5-(4-methoxyphenyl)-2H-1,2,3-triazole-4-
carboxylate (2f): Prepared from 1f (125 mg, 0.3 mmol)
and NaN3 (0.315 mmol, 20.5 mg). White solid; yield 76
mg, 96%; m.p. 81 — 82 ℃ ; V(petroleum ether) ∶
1
V(ethyl acetate)＝2∶1, Rf＝0.3; H NMR (400 MHz,
CDCl3) δ: 7.80 (d, J＝8.8 Hz, 2H), 6.97 (d, J＝8.8 Hz,
2H), 5.25—5.32 (m, 1H), 3.86 (s, 3H), 1.34 (d, J＝6.4
Hz, 6H); 13C NMR (100 MHz, CDCl3) δ: 160.7, 130.7,
113.7, 69.5, 55.3, 21.7; HRMS (ESI) calcd for
C13H15N3O3 [M＋Na]＋ 284.1011, found 284.1041.
Isopropyl 5-(4-bromophenyl)-2H-1,2,3-triazole-4-
carboxylate (2g): Prepared from 1g (140 mg, 0.3 mmol)
and NaN3 (0.32 mmol, 21 mg). White solid; yield 88 mg,
95%; m.p. 121—122 ℃ ; V(petroleum ether)∶V(ethyl
acetate)＝2∶1, Rf＝0.3; 1H NMR (400 MHz, CDCl3) δ:
7.76 (d, J＝8.4 Hz, 2H), 7.60 (d, J＝8.4 Hz, 2H), 5.28
—5.34 (m, 1H), 1.37 (d, J＝6.4 Hz, 6H); 13C NMR (100
MHz, CDCl3) δ: 131.5, 130.9, 124.0, 70.0, 40.4, 21.7;
HRMS (ESI) calcd for C12H12BrN3O2 [M ＋ Na] ＋
332.0011, found 332.0042.
Isopropyl 5-(2,4-dimethoxyphenyl)-2H-1,2,3-tria-
zole-4-carboxylate (2b): Prepared from 1b (134 mg, 0.3
mmol) and NaN3 (0.32 mmol, 21 mg). Pale yellow solid;
yield 83 mg, 95%; m.p. 151—152 ℃; V(petroleum
1
ether)∶V(ethyl acetate)＝1∶1, Rf＝0.3; H NMR (400
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© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2012, 30, 2786—2790

Facile Synthesis of 4,5-Disubstituted 2H-1,2,3-Triazoles by Catalyst-free Cycloaddition
Isopropyl
5-(furan-2-yl)-2H-1,2,3-triazole-4-car-
127.8, 127.7, 127.0, 126.5, 69.7, 21.7; HRMS (ESI)
calcd for C16H15N3O2 [M ＋ Na] ＋ 304.1062, found
304.1078.
boxylate (2h): Prepared from 1h (113 mg, 0.3 mmol)
and NaN3 (0.32 mmol, 21 mg). Yellow oil; yield 63 mg,
95%; V(petroleum ether)∶V(ethyl acetate)＝2∶1, Rf＝
0.3; 1H NMR (400 MHz, CDCl3) δ: 7.61 (s, 1H), 7.56 (s,
1H), 6.58 (m, 1H), 5.33—5.39 (m, 1H), 1.41 (d, J＝6.4
Hz, 6H); 13C NMR (100 MHz, CDCl3) δ: 160.4, 144.0,
114.5, 112.1, 69.6, 21.8; HRMS (ESI) calcd for
C10H11N3O3 [M＋Na]＋ 244.0698, found 244.0717.
Isopropyl 5-p-tolyl-2H-1,2,3-triazole-4-carboxylate
(2i): Prepared from 1i (121 mg, 0.3 mmol ) and NaN3
(0.32 mmol, 21 mg). White solid; yield 72 mg, 98%;
m.p. 70—71 ℃; V(petroleum ether)∶V(ethyl acetate)
＝2∶1, Rf＝0.3; 1H NMR (400 MHz, CDCl3) δ: 7.72 (d,
J＝8.0 Hz, 2H), 7.26 (d, J＝8.0 Hz, 2H), 5.26—5.32 (m,
1H), 2.41 (s, 3H), 1.34 (d, J＝6.0 Hz, 6H); 13C NMR
(100 MHz, CDCl3) δ: 160.8, 139.8, 129.2, 129.0, 69.5,
21.7, 21.4; HRMS (ESI) calcd for C13H15N3O2 [M＋
Na]＋ 268.1062, found 268.1078.
Isopropyl 5-(naphthalen-1-yl)-2H-1,2,3-triazole-4-
carboxylate (2j): Prepared from 1j (131 mg, 0.3 mmol)
and NaN3 (0.32 mmol, 21 mg). Colourless oil; yield 83
mg, 98%; V(petroleum ether)∶V(ethyl acetate)＝2∶1,
Rf＝0.3; 1H NMR (400 MHz, CDCl3) δ: 7.59—7.89 (m,
2H), 7.60—7.43 (m, 5H), 4.97—5.03 (m, 1H), 0.94 (d,
J＝6.4 Hz, 6H); 13C NMR (100 MHz, CDCl3) δ: 160.5,
133.3, 131.9, 129.8, 128.4, 128.3, 126.5, 126.1, 125.3,
124.8, 69.2, 21.2; HRMS (ESI) calcd for C16H15N3O2
[M＋ Na]＋ 304.1062, found 304.1076.
Isopropyl 5-o-tolyl-2H-1,2,3-triazole-4-carboxylate
(2n): Prepared from 1n (121 mg, 0.3 mmol) and NaN3
(0.32 mmol, 21 mg). White solid; yield 70 mg, 95%;
m.p. 88—89 ℃; V(petroleum ether)∶V(ethyl acetate)
＝2∶1, Rf＝0.3; 1H NMR (400 MHz, CDCl3) δ: 7.38—
7.34 (m, 1H), 7.29—7.22 (m, 3H), 5.13—5.19 (m, 1H),
2.16 (s, 3H), 1.20 (d, J＝6.4 Hz, 6H); 13C NMR (100
MHz, CDCl3) δ: 160.5, 137.4, 130.2, 130.1, 129.5,
125.4, 69.2, 21.6, 19.9; HRMS (ESI) calcd for
C13H15N3O2 [M＋ Na]＋ 268.1062, found 268.1076.
Isopropyl 5-heptyl-2H-1,2,3-triazole-4-carboxylate
(2o): Prepared from 1o (123 mg, 0.3 mmol) and NaN3
(0.32 mmol, 21 mg). Yellow oil; yield 73 mg, 96%;
V(petroleum ether)∶V(ethyl acetate)＝2∶1, Rf＝0.3;
1H NMR (400 MHz, CDCl3) δ: 5.33 (m, 1H), 3.03 (t,
J＝7.6 Hz, 2H), 1.70—1.73 (m, 2H), 1.40 (d, J＝6.4 Hz,
6H), 1.23—1.37 (m, 8H), 0.89 (t, J＝6.4 Hz, 3H); 13C
NMR (100 MHz, CDCl3) δ: 161.2, 69.0, 31.7, 29.3, 29.0,
29.0, 22.6, 21.9, 14.1; HRMS (ESI) calcd for
C13H23N3O2 [M＋ Na]＋ 276.1688, found 276.1720.
Acknowledgement
We acknowledge the financial support from the
National Natural Science Foundation of China (No.
21172072), the Shanghai Natural Science Foundation
(No. 11ZR1408500) and the Shanghai Committee of
Science and Technology (Grant 11DZ2260600).
Isopropyl
5-(4-fluorophenyl)-2H-1,2,3-triazole-4-
carboxylate (2k): Prepared from 1k (122 mg, 0.3 mmol)
and NaN3 (0.32 mmol, 21 mg). White solid; yield 72 mg,
96%; m.p. 128—129 ℃; V(petroleum ether)∶V(ethyl
acetate)＝2∶1, Rf＝0.3; 1H NMR (400 MHz, CDCl3) δ:
7.88—7.85 (m, 2H), 7.17—7.13 (m, 2H), 5.27—5.34
(m, 1H), 1.35 (d, J＝6.4 Hz, 6H); 13C NMR (100 MHz,
CDCl3) δ: 164.7, 162.3, 160.6, 131.4, 131.3, 115.5,
115.2, 69.9, 21.7; HRMS (ESI) calcd for C12H12FN3O2
[M＋Na]＋ 272.0811, found 272.0829.
Isopropyl 5-(3-bromophenyl)-2H-1,2,3-triazole-4-
carboxylate (2l): Prepared from 1l (140 mg, 0.3 mmol)
and NaN3 (0.32 mmol, 21 mg). White solid; yield 83 mg,
90%; m.p. 124—125 ℃ ; V(petroleum ether)∶V(ethyl
acetate)＝2∶1, Rf＝0.3; 1H NMR (400 MHz, CDCl3) δ:
8.05 (s, 1H), 7.83 (d, J＝7.6 Hz, 1H), 7.59 (d, J＝8.0
Hz, 1H), 7.35 (t, J＝8.0 Hz, 1H), 5.31—5.37 (m, 1H),
1.38 (d, J＝6.4 Hz, 6H); 13C NMR (100 MHz, CDCl3) δ:
160.5, 132.4, 130.6, 129.8, 128.0, 122.1, 70.2, 21.7;
HRMS (ESI) calcd for C12H12BrN3O2 [M ＋ Na] ＋
332.0011, found 331.0958.
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1
2∶1, Rf＝0.3; H NMR (400 MHz, CDCl3) δ: 8.37 (s,
1H), 7.90—7.86 (m, 4H), 7.55—7.54 (m, 2H), 5.29—
5.35 (m, 1H), 1.34 (d, J＝6.0 Hz, 6H); 13C NMR (100
MHz, CDCl3) δ: 160.7, 133.6, 132.8, 129.2, 128.5,
Chin. J. Chem. 2012, 30, 2786—2790
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2790
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© 2012 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2012, 30, 2786—2790