Synthesis of N-(2-Hydroxyaryl)benzotriazoles via Metal-Free O-Arylation and N-O Bond Cleavage

Article abstract of DOI:10.1021/acs.joc.6b01390

A metal-free method for synthesis of N-(2-hydroxyaryl)benzotriazoles via O-arylation of N-hydroxybenzotriazoles with readily available diaryliodonium salts and sequential N-O bond cleavage under mild conditions has been developed. The [3,3]-rearrangement of N-O bond cleavage could take place on the N instead of C atom. The reaction was compatible with diverse functional groups and a new type of P,N-ligand was synthesized in three steps.

Full text of DOI:10.1021/acs.joc.6b01390

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Note
Synthesis of N-(2-Hydroxyaryl)-Benzotriazoles via
Metal-Free O-Arylation and N-O Bond Cleavage
Zhi-Xin Wang, Wei-Min Shi, Hong-Yan Bi, Xiao-Hua Li, Gui-Fa Su, and Dong-Liang Mo
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.6b01390 • Publication Date (Web): 08 Aug 2016
Downloaded from http://pubs.acs.org on August 10, 2016
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Synthesis of N-(2-Hydroxyaryl)-Benzotriazoles via Metal-Free
O-Arylation and N-O Bond Cleavage
7
8
9
ZhiꢀXin Wang, WeiꢀMin Shi, HongꢀYan Bi, XiaoꢀHua Li, GuiꢀFa Su*, and
DongꢀLiang Mo*
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State Key Laboratory for Chemistry and Molecular Engineering of Medicinal
Resources, Ministry of Science and Technology of China; School of Chemistry &
Pharmaceutical Sciences, Guangxi Normal University, 15 Yu Cai Road, Guilin
541004, China.
3
N
N
C
N
N
3
2
N
N
N
R
[3,3]
N
Ar2IOTf
R
2
N
1
R
C
3'
1
16 examples
43-89% yields
OH
C
O
1' 2'
23 examples
OH
40-99% yields
R1
R1
♣
♣High regioselectivity
Metal-free O-arylation
♣Rearrangement on N-atom only
♣Broad substrate scope
ABSTRACT: A metalꢀfree method for synthesis of Nꢀ(2ꢀhydroxyaryl)ꢀbenzotriazoles
via Oꢀarylation of Nꢀhydroxybenzotriazoles with readily available diaryliodonium
salts and sequential N−O bonds cleavage under mild conditions has been developed.
The [3,3]ꢀrearrangement of N−O bond cleavage could take place on Nꢀatom instead of
Cꢀatom. The reaction was compatible with diverse functional groups and a new type
of P, Nꢀligand was synthesized in three steps.
NꢀArylbenzotriazoles are one of the most important classes of Nꢀheterocycles in
biological, pharmaceutical and medicinal chemistry.1a Many these structural motifs
possess antiplasmodial, antibacterial, anticancer, and antifungal activities.1bꢀe They are
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not only used as useful synthons in organic synthesis,2 but also served as elegant
Nꢀligands in transitionꢀmetal catalysis.3 Thus, development of new methods for
construction of the functionalized Nꢀarylbenzotriazoles is an important field in
organic chemistry. There were many strategies for synthesis of Nꢀarylbenzotriazoles
with satisfied yields, such as transitionꢀmetal catalyzed crossꢀcoupling reaction,4
palladium catalyzed C−H activation of aryltriazene compounds,5 or relative
transformations.6 However, there was few efficient methods to prepare
Nꢀ(2ꢀhydroxyaryl)ꢀbenzotriazoles, which were also important scaffolds served as
potassium channel activator and attracted in biological sciences (Figure 1). Only in
2001, Livi and coworkers demonstrated that Nꢀ(2ꢀhydroxyphenyl)ꢀbenzotriazole can
be prepared from anthranilic acid followed by cycloaddition with 2ꢀnitrophenylazide
or 2ꢀhydroxyphenylazide in 28% and 54% yields respectively (Scheme 1ꢀ1).7
Although a successful route to synthesize Nꢀ(2ꢀhydroxyphenyl)ꢀbenzotriazole was
developed, low yields and only one substrate has been shown. Hence, to explore an
efficient strategy to synthesize these compounds is desirable.
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N
N
N
N
N
N
Cl
OH
O
Antiplasmodial agent
Potassium channel activator
O
N
HN
N
N
Me
Me
OCF3
O
c-Kit Protooncogene inhibitor
Figure 1. Some examples of biologically active scaffolds.
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In the N−O bond system, the rearrangement was always preferably taken place on
Cꢀatom of aryl ring instead of Nꢀatom or gave a mixture.8 A recent example was
reported by Hammond and Xu group in 2013.8a The authors developed a
goldꢀcatalyzed intermolecular addition of Nꢀhydroxybenzotriazoles to terminal
alkynes to give vinyl ethers in high yields and excellent regioselectivity, which
preferably underwent a [3,3]ꢀsigmatropic rearrangement on Cꢀatom to provide highly
functionalized benzotriazoles (Scheme 1ꢀ2). During the studies of arylation of N−O
bonds with diaryliodonium salts in our group,9,10 we have reported an efficient
method to synthesize Nꢀaryl benzotriazinꢀ4ꢀones by Oꢀarylation and
[3,3]ꢀrearrangement.9b The [3,3]ꢀrearrangement of Oꢀarylation products only took
place on Nꢀatom instead of Oꢀatom. Continuing to explore the rearrangement of
Oꢀarylation products in Nꢀhydroxybenzotriazoles, we observed that the rearrangement
of N−O bond only took place on Nꢀatom instead of Cꢀatom. Hence, arylation of
Nꢀhydroxybenzotriazoles to form Oꢀarylation products and sequential regioselective
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[3,3]ꢀrearrangement
on
Nꢀatom
will
provide
diverse
useful
Nꢀ(2ꢀhydroxyaryl)ꢀbenzotriazoles. Although Oꢀarylation product has been obtained by
Chan and coworkers via copperꢀmediated crossꢀcoupling of Nꢀhydroxybenzotriazole
and arylboronic acid, only one example has been shown and no rearrangement
product was reported.11 Herein, we reported a simple, mild, and efficient metalꢀfree
strategy to prepare Nꢀ(2ꢀhydroxyphenyl)ꢀbenzotriazoles (Scheme 1ꢀ3).
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1) Multi-steps including cycloaddition, Sandmyer reaction
N3
NO2
N
N
NH2
N
NO2
[3+2]
7
COOH
8
9
N3
[3+2]
Pd/H2
OH
N
N
N
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N
N
N
NaNO2
H2SO4/H2O
NH2
OH
2) Gold-catalyzed O-vinylation and rearrangement on C-atom
H
N
N
N
R
N
N
R
40-75%
N
[3,3]
[Au]
N
N
R
N
+
O
R1
53-100%
O
R1
17 examples
OH
R1
6 examples
3) This work: metal-free O-arylation and controllable rearrangement on N-atom
N
N
R
R1
R
on C-atom
N
C
H
N
N
OH
N
N
N
R
Ar2IOTf
N
R
C
O
C
OH
N
N
R1
on N-atom
N
OH
R1
Scheme 1. Strategies for synthesis of orthoꢀ(benzotriazolꢀ1ꢀyl)phenols
In order to investigate the rearrangement of Oꢀarylation intermediate, the reaction
conditions of Oꢀarylation were optimized. Firstly, Nꢀhydroxybenzotriazole 1a with
diphenyliodonium triflate 2a was used as model substrates in different solvents, base
and temperature (Table 1). The reaction occurred to afford the desired Oꢀarylation
product 3aa in 81% yield in DCE (1,2ꢀdichloroethane) when tꢀBuOK was used as
base (Table 1, entry 1). The solvents such as MeOH and THF gave inferior results
(Table 1, entries 4 and 5). Higher yields were obtained in toluene, MeCN, dioxane,
DMF and DMSO (Table 1, entries 2ꢀ3 and 6ꢀ8). MeCN was chosen as the best solvent
for Oꢀarylation (Table 1, entry 3). The reaction was effective with tꢀBuOK, KOH,
Cs2CO3, NaHCO3, and Et3N (Table 1, entries 9ꢀ13), and only 20% yield of 3aa was
observed using pyridine (Table 1, entry 12). When the reaction ran at 40 °C, 3aa was
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obtained in 55% yield and 3aa was not detected while the reaction temperature was at
80 °C (Table 1, entries 3 and 14ꢀ16). Further controlled experiments confirmed that
no 3aa was afforded in the absence of base (Table 1, entry 17). To our delight, when
1a was enlarged to 2.5 mmol in MeCN, product 3aa was isolated in 98% yield (Table
1, entry 3). Hence, the optimal conditions were that tꢀBuOK was used as base in
MeCN at 25 °C for 18 h.
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Table 1. Optimization of reaction conditions.a
N
N
Conditions
N
N
+
Ph2IOTf
N
N
OH
O
Ph
1a
2a
3aa
entry
base
solvent
3aa % b
81
T (°C
)
1
tꢀBuOK
tꢀBuOK
tꢀBuOK
tꢀBuOK
tꢀBuOK
tꢀBuOK
tꢀBuOK
tꢀBuOK
KOH
DCE
25
25
25
25
25
25
25
25
25
25
25
25
2
toluene
MeCN
MeOH
THF
72
3
99(98)c
12
4
5
54
6
dioxane
DMF
90
7
96
8
DMSO
MeCN
MeCN
MeCN
MeCN
74
9
95
10
11
12
Cs2CO3
NaHCO3
pyridine
95
42
20
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MeCN
MeCN
MeCN
MeCN
MeCN
25
40
60
80
80
97
55
20
<5
0
Et3N
tꢀBuOK
tꢀBuOK
tꢀBuOK
ꢀ
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a Reaction conditions: 1a (0.5 mmol), 2a (0.75 mmol, 1.5 equiv), base (0.75 mmol,
1.5 equiv), solvent (5 mL), 18−24 h; b Isolated yields. c 1a was used as 2.5 mmol.
Next, the scope of present protocols was studied for diaryliodonium salts having
substituents on the aryl rings. As shown in Table 2, both electronꢀrich and
electronꢀdeficient diaryliodonium salts 2, with para, meta, or orthoꢀsubstituents
provided the corresponding products 3aa-3am in good to excellent yields. The
electronꢀdonating groups such as methoxy, methyl gave lower yields of Oꢀarylation
products (Table 2, entries 2ꢀ3), and the major products were the [3,3]ꢀrearrangement
products which have been developed as oneꢀpot reaction (see Table 5). When
unsymmetrical diaryliodonium salts were tested, the Oꢀarylation reaction proceeded
smoothly with good chemoselectivity and electronꢀdeficient aryl moieties were
preferentially transferred to product 3 (Table 2, entries 9ꢀ14).12 The bromo, chloro,
nitro, and ester functional groups were all well tolerated for the iodonium reagents in
this transformation.
Table 2. The scope of diaryliodonium salts 2.a
N
N
N
N
I
OTf
R2
t-BuOK
N
N
+
R1
RT
O
OH
R1
1a
2
3
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entry
1
2
R1
R2
3
yield %b
99
2a
2b
2c
2d
2e
2f
H
H
3aa
3ab
3ac
3ad
3ae
2
4ꢀMeO
4ꢀMe
4ꢀCl
4ꢀMeO
4ꢀMe
4ꢀCl
4ꢀF
<5
40
3
4
82
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5
4ꢀF
57
6
3,5ꢀMe2
3ꢀNO2
2ꢀMe
H
3,5ꢀMe2 3af
89
7
2g
2h
2aa
2i
3ꢀNO2
2ꢀMe
3ag
3ah
3aa
3ai
92
8
65
9
4ꢀMeO
4ꢀMeO
4ꢀMeO
4ꢀMeO
4ꢀMeO
H
92
10
11
12
13
14
4ꢀPh
4ꢀBr
3ꢀBr
2ꢀBr
4ꢀCO2Me
61
2j
3aj
83
2k
2l
3ak
3al
81
68
2m
3am
90
a Reaction conditions: 1a (0.5 mmol), 2 (0.75 mmol, 1.5 equiv), tꢀBuOK (0.75 mmol,
1.5 equiv), MeCN (5 mL), 25 °C, 18−24 h; b Isolated yields.
In addition to screening the diaryliodonium salts, a variety of substituted
Nꢀhydroxybenzotriazoles were examined (Table 3). We found that product 3 was
afforded in good to excellent yields when substituted Nꢀhydroxybenzotriazoles with
both electronꢀrich groups (Table 3, entries 2ꢀ3) and electronꢀdeficient groups were
subjected into the optimal conditions (Table 3, entries 4ꢀ7). Moreover,
Nꢀhydroxyꢀ7ꢀazabenzotriazole 1h and Nꢀhydroxyꢀ4ꢀazabenzotriazole 1i provided
desired product 3ha and 3ia in 90% yield and 60% yield respectively (Table 3, entries
8 and 9). However, when there were methyl and chloro substituents in 5ꢀposition of 1
such as 1j and 1k, the yields decreased to moderate (Table 3, entries 10ꢀ11).
Table 3. The scope of Nꢀhydroxybenzotriazoles 1 a,b
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3
N
4
5
6
N
N
2
t-BuOK
R
N
1
N
R
+
Ph2IOTf
N
RT
X
7
X
OH
O
Ph
1
3aa-3ka
X= C, N
9
entry
1
3
yield%
99
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N
N
N
N
N
N
1
2
3
4
5
6
1a
1b
1c
1d
1e
1f
3aa
3ba
3ca
3da
3ea
3fa
O
OH
Ph
N
N
N
N
N
N
99
MeO
Me
MeO
O
Ph
OH
N
N
N
N
N
86
N
Me
Cl
O
Ph
OH
N
N
N
N
N
N
81
Cl
O
OH
Ph
N
N
N
N
N
N
74
F3
C
F3C
O
OH
Ph
N
N
N
N
N
N
62
NC
NC
O
OH
Ph
Cl
Cl
N
N
N
N
N
N
7
1g
3ga
50
O
OH
Ph
N
N
N
N
N
8
9
1h
1i
3ha
3ia
90
60
36
43
N
N
N
N
O
OH
Ph
N
N
N
N
N
N
N
O
Ph
N
OH
Me
Cl
Me
Cl
N
N
N
N
10
11
1j
3ja
3ka
N
O
Ph
OH
N
N
N
N
N
N
1k
O
OH
Ph
a Reaction conditions: 1 (0.5 mmol), 2a (0.75 mmol, 1.5 equiv), tꢀBuOK (0.75 mmol,
1.5 equiv), MeCN (5 mL), 25 °C, 18−24 h; b Isolated yields.
With the Oꢀarylation products in hand, the N−O rearrangement reaction was
investigated. When various substrates 3 were subjected to MeCN at 60 °C,13 the
desired rearrangement products 4 were obtained in 43ꢀ89% yields (Table 4). The
results showed that the rearrangement only took place on Nꢀatom instead of Cꢀatom.
The reaction ran smoothly with both electronꢀdonating groups and
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electronꢀwithdrawing groups on both aryl rings. The regioselectivity of
[3,3]ꢀrearrangement was excellent when R1 group was 3ꢀNO2 substituent (Table 4,
entry 4). The functional groups were tolerated well, such as bromide, chloride, nitro,
and ester groups which will make more potential synthetic applications of
Nꢀ(2ꢀhydroxyaryl)ꢀbenzotriazoles. For products 4aa-am, the [3,3] and
[1,3]ꢀrearrangement structures were the same products so that it was hard to
determine the selectivity of [3,3] and [1,3]ꢀrearrangement (Table 4, entries 1ꢀ7). When
there were substituted groups on aryl ring of benzotriazole moiety in 3, a mixed
product of [3,3] and [1,3]ꢀrearrangement on Nꢀatom was obtained. The ratio of
rearrangement products was depended on the substituted groups (Table 4, entries
9ꢀ13). The structure of [3,3] and [1,3]ꢀrearrangement products was determined by 2D
NMR spectra of 4ba-ka. When there was Nꢀatom on 7ꢀposition in 3ha, the
rearrangement still occurred on N3ꢀatom (Table 4, entry 8). Both electronꢀdonating
and electronꢀwithdrawing groups gave [3,3]ꢀrearrangement products as major isomers
except for 3ba with a methoxy group on 6ꢀposition providing the [3,3]ꢀrearrangement
and [1,3]ꢀrearrangement product as 1:1 ratio (Table 4, entries 9 vs 10ꢀ13).
10
11
12
13
14
15
16
17
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19
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Table 4. The thermal rearrangement of Oꢀarylation product 3 a,b
X
3
4
N
N
N
N
N
5
6
R
R
N
N
2
MeCN, 60 °C
R
N
X
+
OH
OH
N
1
X
7
O
R1
R1
R1
3
4
4'
[1,3]-product
X= C, N
[3,3]-product
entry
3
R
H
H
H
R1
H
4
yield %
1
2
3
3aa
3ac
3af
4aa
4ac
4af
70
52
71
4ꢀMe
3,5ꢀMe2
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3ag
3ah
3aj
H
H
3ꢀNO2
2ꢀMe
4ꢀBr
4ag 57 (20:1)c
4ah
4aj
57
57
86
6
H
7
3am
3ha
3ba
3da
3ea
3ja
H
4ꢀCO2Me 4am
8
H
H
H
H
H
H
H
4ha 61 (20:1)d
4ba
85 (1:1)d
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6ꢀOMe
6ꢀCl
6ꢀCF3
5ꢀMe
5ꢀCl
10
11
12
13
4da 89 (10:1)d
4ea 81 (10:1)d
4ja 63 (10:1)d
4ka 43 (10:1)d
3ka
a Reaction conditions: 3 (0.5 mmol), MeCN (5 mL), 60 °C, 18ꢀ24 h; b Isolated yields;
c
d
regioselectivity for [3,3]ꢀrearrangement on aryl ring, >20:1;
[3,3]ꢀproduct and [1,3]ꢀproduct.
the ratio of
During the study of the scope of diaryliodonium salts in Table 2, we found
iodonium reagents with electronꢀdonating groups only gave the rearrangement
product instead of Oꢀarylation product (Table 2, entry 2), which inspired us to develop
oneꢀpot
reaction
to
prepare
Nꢀ(2ꢀhydroxyaryl)ꢀbenzotriazoles
from
Nꢀhydroxybenzotriazole 1 with iodonium reagent 2. The results were summarized in
Table 5. It showed that the reaction tolerated well for Nꢀhydroxybenzotriazoles and
diaryliodonium salts. In contrast to Table 4, the ratios of [3,3]ꢀ and
[1,3]ꢀrearrangement products were the same either by two steps or oneꢀpot reaction
(Table 4 vs Table 5, 4da and 4ea). However, when diaryliodonium salt 2b was used,
the ratio of [3,3]ꢀ and [1,3]ꢀrearrangement products turned bad (Table 5, entries 6ꢀ8).
Table 5. Synthesis of Nꢀ(2ꢀhydroxyaryl)ꢀbenzotriazole 4 in oneꢀpot reaction a
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N
4
7
3
N
R
5
N
2
N
R
N
N
1
OH
t-BuOK
OH
+
Ar2IOTf
6
MeCN, 60 °C
R1
1 (1a, 1d-e)
2 (2a, 2b, 2n)
4
9
entry
1
2
Ar
Ph
4
yield %b
69
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1
2
3
4
5
6
7
8
1a
1a
1a
1d
1e
1c
1d
1f
2a
2b
2n
2a
2a
2b
2b
2b
4aa
4ab
4an
4da
4ea
4cb
4db
4fb
4ꢀMeOC6H4
79
4ꢀ
t
ꢀBuC6H4
Ph
82
68 (10:1)c
64 (10:1)c
85 (2.5:1)c
64 (1.4:1)c
50 (1:1)c
Ph
4ꢀMeOC6H4
4ꢀMeOC6H4
4ꢀMeOC6H4
a
Reaction conditions: 1 (0.5 mmol), 2 (0.75 mmol, 1.5 equiv), tꢀBuOK (0.75 mmol,
b
c
1.5 equiv), MeCN (5 mL), 60 °C, 18ꢀ24 h;
Isolated yields; The ratio of
[3,3]ꢀrearrangement and [1,3]ꢀrearrangement products.
To better apply this process in synthetic transformations, a gram scale of 1a was
subjected to the optimal conditions, the desired product 4aa was afforded in 67%
yield with 1.41 g (Scheme 2ꢀ1). Treatment of 4aa with iodonium reagent 2l under
tꢀBuOK in DCE at room temperature provided Oꢀarylation product 5 in 83% yield,
which was easily converted to P, Nꢀligand 6 in 40% yield. This method will allow
further studies on this type of P, Nꢀligand containing benzotriazole in transitionꢀmetal
catalysis (Scheme 2ꢀ2).3c,d
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1) Gram preparation of 4aa
N
N
N
N
t-BuOK
N
OH
Ph2IOTf
+
N
MeCN, 60 °C
OH
1a (1.35 g, 10 mmol)
4aa (1.41 g, 67% yield)
2) Synthesis of P, N-ligand 6
N
N
N
N
N
Br
Ph2P
N
N
i)
N
ii)
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N
O
O
OH
40% yield
83% yield
4aa
5
6
Conditions: i) t-BuOK, 2l (1.5 equiv), DCE, 18-24 h
ii) n-BuLi, PPh2Cl, THF, 18 h
Scheme 2 Application of 4aa
In summary, we have developed
a
metalꢀfree strategy to prepare
Nꢀ(2ꢀhydroxyaryl)ꢀbenzotriazoles from good to excellent yields under mild conditions.
The reaction not only went through Oꢀarylation and sequential [3,3]ꢀrearrangement in
two steps, but also could run in oneꢀpot reaction in good yields. It was compatible
with lots of functional groups as well as Nꢀheterocycle substrates.
Nꢀ(2ꢀHydroxyaryl)ꢀbenzotriazoles could be easily converted to a new type of P,
Nꢀligand in two steps.
EXPERIMENTAL SECTION
General Methods. All reactions were performed under an atmosphere of air.
Commercially available reagents were used without further purification. The NMR
spectra were recorded in CDCl3 or DMSOꢀd6 on 400 MHz, or 500 MHz instrument
with TMS as the internal standard. NMR data are represented as follows: chemical
shift (ppm), multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, m =
multiplet), coupling constants in hertz (Hz), and integration. IR spectra were recorded
on FTꢀIR spectrometer, and only major peaks are reported in cm‒1. HRMS were
measured in ESI mode and the mass analyzer of the HRMS was TOF. Flash column
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chromatography was performed on silica gel (300−400 mesh).
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General procedure for synthesis of O-arylation products 3 (Table 2 and Table
3): In a 25 mL Schlenk tube was charged with 1 (0.5 mmol) and MeCN (5 mL).
tꢀBuOK (0.75 mmol, 1.5 equiv) was added in one portion at room temperature. The
mixture was stirred vigorously at room temperature for 5 min. Then, diaryliodonium
salts 2 (0.75 mmol, 1.5 equiv) was added in one portion. The reaction mixture was
stirred vigorously at room temperature for 18−24 h until the substrate 1 disappeared
(monitored by TLC). At this time, the solvent was removed under reduced pressure
and the crude product was purified by flash chromatography (the crude residue was
dry loaded on silica gel; 1 / 20 − 1 / 5, ethyl acetate / petroleum ether) to provide
product 3 as solid.
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1-Phenoxy-1H-benzo[1,2,3]triazole (3aa), white solid, 0.104 g, 99% yield. mp:
1
64−65 °C; H NMR (500 MHz, CDCl3): δ 8.02 (d, J = 8.5 Hz, 1H), 7.45 (d, J = 3.0
Hz, 2H), 7.38−7.35 (m, 1H), 7.28 (t, J = 8.0 Hz, 2H), 7.12 (t, J = 7.5 Hz, 1H), 6.86 (d,
J = 8.0 Hz, 2H); 13C NMR (125 MHz, CDCl3): δ 159.2, 143.4, 129.9, 128.6, 127.7,
125.2, 124.9, 120.4, 113.9, 108.7; IR (thin film) 3415, 3064, 2876, 1782, 1486, 1376,
1243, 1084, 744, 681 cm−1; HRMS (ESI) m/z calcd for C12H10N3O (M+H)+ 212.0824,
found 212.0815.
1-(p-Tolyloxy)-1H-benzo[d][1,2,3]triazole (3ac)11, white solid, 0.045 g, 40% yield.
1
mp: 58−59 °C; H NMR (400 MHz, CDCl3): δ 8.08 (d, J = 7.2 Hz, 1H), 7.52 (d, J =
5.0 Hz, 2H), 7.44−7.42 (m, 1H), 7.13 (d, J = 6.4 Hz, 2H), 6.87 (d, J = 7.2 Hz, 2H),
2.31 (s, 3H); 13C NMR (125 MHz, CDCl3): δ 157.3, 143.4, 135.0, 130.3, 128.5, 127.7,
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124.8, 120.4, 114.1, 108.7, 20.6; IR (thin film) 3435, 3036, 2923, 1602, 1501, 1374,
1238, 1083, 801, 749 cm−1; HRMS (ESI) m/z calcd for C13H12N3O (M+H)+ 226.0980,
found 226.0950.
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1-(4-Chlorophenoxy)-1H-benzo[d][1,2,3]triazole (3ad), white solid, 0.100 g, 82%
1
yield. mp: 55−56 °C; H NMR (500 MHz, CDCl3): δ 8.11 (d, J = 8.0 Hz, 1H),
7.57−7.50 (m, 2H), 7.47 (t, J = 7.5 Hz, 1H), 7.32 (d, J = 8.5 Hz, 2H), 6.92 (d, J = 8.5
Hz, 2H); 13C NMR (125 MHz, CDCl3): δ 157.7, 143.4, 130.0, 128.8, 125.1, 120.8,
115.6, 108.5; IR (thin film) 3418, 3069, 1616, 1483, 1373, 1238, 1081, 818, 737 cm−1;
HRMS (ESI) m/z calcd for C12H7N3ClO (M−H)− 244.0278, found 244.0283.
1-(4-Fluorophenoxy)-1H-benzo[d][1,2,3]triazole (3ae), white solid, 0.065 g, 57%
1
yield. mp: 51−52 °C; H NMR (500 MHz, CDCl3): δ 8.10 (d, J = 8.5 Hz, 1H),
7.56−7.55 (m, 2H), 7.47−7.44 (m, 1H), 7.06 (t, J = 8.5 Hz, 2H), 7.00−6.98 (m, 2H);
13C NMR (125 MHz, CDCl3): δ 160.7 (d, J = 243.2 Hz), 155.1, 143.4, 128.8, 127.5,
125.0, 120.5, 116.7 (d, J = 23.7 Hz), 116.2 (d, J = 8.2 Hz), 108.5; IR (thin film) 3419,
3073, 2977, 1614, 1499, 1378, 1230, 1082, 833, 738 cm−1; HRMS (ESI) m/z calcd for
C12H9N3OF (M+H)+ 230.0730, found 230.0722.
1-(3,5-Dimethylphenoxy)-1H-benzo[d][1,2,3]triazole (3af), white solid, 0.106 g,
1
89% yield. mp: 53−54 °C; H NMR (400 MHz, CDCl3): δ 8.09 (d, J = 8.0 Hz, 1H),
7.53 (t, J = 2.4 Hz, 2H), 7.45−7.42 (m, 1H), 6.80 (s, 1H), 6.56 (s, 2H), 2.25 (s, 6H);
13C NMR (100 MHz, CDCl3): δ 159.4, 143.5, 140.1, 128.5, 127.8, 126.9, 124.8, 120.4,
111.7, 108.8, 21.3; IR (thin film) 3416, 3060, 2920, 1781, 1451, 1375, 1278, 1082,
837, 742 cm−1; HRMS (ESI) m/z calcd for C14H13N3ONa (M+Na)+ 262.0956, found
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262.0945.
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1-(3-Nitrophenoxy)-1H-benzo[d][1,2,3]triazole (3ag), yellowish solid, 0.118 g, 92%
yield. mp: 105−106 °C; 1H NMR (500 MHz, CDCl3): δ 8.15 (d, J = 8.5 Hz, 1H), 8.10
(d, J = 8.0 Hz, 1H), 7.83 (s, 1H), 7.62−7.49 (m, 4H), 7.30−7.28 (m, 1H); 13C NMR
(125 MHz, CDCl3): δ 159.3, 149.1, 143.4, 131.0, 129.3, 127.5, 125.4, 120.7, 120.1,
120.0, 109.6, 108.2; IR (thin film) 3423, 3098, 2924, 1727, 1532, 1349, 1276, 1081,
766, 736 cm−1; HRMS (ESI) m/z calcd for C12H7O3N4 (M−H)− 255.0518, found
255.0525.
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1-(o-Tolyloxy)-1H-benzo[d][1,2,3]triazole (3ah), white solid, 0.073 g, 65% yield.
mp: 58−59 °C; 1H NMR (500 MHz, CDCl3): δ 8.02 (d, J = 8.5 Hz, 1H), 7.45−7.44 (m,
2H), 7.37 (t, J = 7.5 Hz, 1H), 7.06 (t, J = 8.5 Hz, 2H), 6.79 (t, J = 8.5 Hz, 2H), 2.24 (s,
3H); 13C NMR (125 MHz, CDCl3): δ 157.3, 143.4, 135.0, 130.3, 128.5, 127.7, 124.8,
120.4, 114.1, 108.7, 20.6; IR (thin film) 3415, 3063, 2981, 1776, 1486, 1375, 1266,
1083, 835, 743 cm−1; HRMS (ESI) m/z calcd for C13H10N3O (M−H)− 224.0824, found
224.0829.
1-(Biphenyl-4-yloxy)-1H-benzo[d][1,2,3]triazole (3ai), white solid, 0.075 g, 61%
1
yield. mp: 121−122 °C; H NMR (500 MHz, CDCl3): δ 8.05 (d, J = 8.5 Hz, 1H),
7.49−7.44 (m, 6H), 7.39−7.34 (m, 3H), 7.29 (t, J = 7.0 Hz, 1H), 6.95 (t, J = 8.5 Hz,
2H); 13C NMR (125 MHz, CDCl3): δ 158.7, 143.4, 139.7, 138.5, 128.8, 128.7, 128.6,
127.7, 127.4, 126.9, 125.0, 120.5, 114.4, 108.7; IR (thin film) 3417, 3065, 2963, 1601,
1484, 1375, 1267, 1083, 754, 695 cm−1; HRMS (ESI) m/z calcd for C18H14N3O
(M+H)+ 288.1137, found 288.1127.
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1-(4-Bromophenoxy)-1H-benzo[d][1,2,3]triazole (3aj), white solid, 0.119 g, 83%
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6
7
1
yield. mp: 55−56 °C; H NMR (400 MHz, CDCl3): δ 8.09 (d, J = 8.0 Hz, 1H),
8
9
7.54−7.51 (m, 2H), 7.49−7.43 (m, 3H), 6.85 (d, J = 8.8 Hz, 2H); 13C NMR (100 MHz,
CDCl3): δ 158.2, 143.3, 132.9, 128.8, 127.5, 125.1, 120.4, 117.9, 115.9, 108.4; IR
(thin film) 3419, 3086, 2960, 1738, 1479, 1370, 1269, 1069, 815, 735 cm−1; HRMS
(ESI) m/z calcd for C12H7N3OBr (M−H)− 287.9772, found 287.9780.
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1-(3-Bromophenoxy)-1H-benzo[d][1,2,3]triazole (3ak), yellow solid, 0.117 g, 81%
1
yield. mp: 56−57 °C; H NMR (500 MHz, CDCl3): δ 8.11 (d, J = 8.5 Hz, 1H),
7.57−7.52 (m, 2H), 7.47−7.44 (m, 1H), 7.34 (d, J = 7.5 Hz, 1H), 7.23−7.19 (m, 1H),
7.15 (s, 1H), 6.88−6.86 (m, 1H); 13C NMR (125 MHz, CDCl3): δ 159.6, 143.4, 131.1,
128.9, 128.5, 127.6, 125.1, 123.2, 120.6, 117.6, 112.8, 108.5; IR (thin film) 3418,
3072, 1788, 1466, 1372, 1265, 1086, 773, 745 cm−1; HRMS (ESI) m/z calcd for
C12H7N3OBr (M−H)− 287.9772, found 287.9780.
1-(2-Bromophenoxy)-1H-benzo[d][1,2,3]triazole (3al), white solid (0.098 g, 68%).
1
mp: 82−83 °C; H NMR (500 MHz, CDCl3): δ 8.09 (d, J = 8.5 Hz, 1H), 7.68 (d, J =
8.0 Hz, 1H), 7.62 (d, J = 8.0 Hz, 1H), 7.56−7.53 (m, 1H), 7.46 (t, J = 8.0 Hz, 1H),
7.19 (d, J = 7.5 Hz, 1H), 7.10 (d, J = 7.5 Hz, 1H), 6.71 (d, J = 8.0 Hz, 1H); 13C NMR
(125 MHz, CDCl3): δ 155.5, 143.3, 134.1, 128.9, 128.8, 127.7, 126.6, 125.1, 120.5,
120.4, 115.5, 108.8; IR (thin film) 3418, 3065, 2961, 1781, 1442, 1371, 1266, 1029,
742, 662 cm−1; HRMS (ESI) m/z calcd for C12H7N3OBr (M−H)− 287.9772, found
287.9779.
Methyl 4-(1H-benzo[d][1,2,3]triazol-1-yloxy)benzoate (3am), white solid, 0.121 g,
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90% yield. mp: 123−124 °C; 1H NMR (400 MHz, CDCl3): δ 8.03 (d, J = 8.0 Hz, 1H),
7.98 (d, J = 8.0 Hz, 2H), 7.48−7.39 (m, 3H), 6.88 (d, J = 8.0 Hz, 2H), 3.82 (s, 3H);
13C NMR (100 MHz, CDCl3): δ 165.8, 162.3, 143.4, 131.9, 129.0, 127.6, 127.1, 125.2,
120.6, 113.4, 108.5, 52.2; IR (thin film) 3417, 2950, 1713, 1436, 1386, 1278, 1108,
752, 685 cm−1; HRMS (ESI) m/z calcd for C14H12O3N3 (M+H)+ 270.0879, found
270.0866.
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6-Methoxy-1-phenoxy-1H-benzo[d][1,2,3]triazole (3ba), white solid, 0.121 g, 99%
yield. mp: 72−73 °C; 1H NMR (400 MHz, CDCl3): δ 7.85 (d, J = 8.6 Hz, 1H), 7.29 (t,
J = 7.2 Hz, 2H), 7.12 (d, J = 7.2 Hz, 1H), 6.98 (d, J = 8.6 Hz, 1H), 6.98 (d, J = 8.0 Hz,
2H), 6.69 (s ,1H), 3.76 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 160.9, 159.2, 138.8,
129.9 129.0, 125.0, 121.2, 117.7, 113.7, 88.3, 55.8; IR (thin film) 3428, 3070, 2958,
1721, 1458, 1346, 1230, 1018, 828, 752 cm−1; HRMS (ESI) m/z calcd for C13H12O2N3
(M+H)+ 242.0930, found 242.0920.
6-Methyl-1-phenoxy-1H-benzo[d][1,2,3]triazole (3ca), white solid, 0.097 g, 86%
yield. mp: 70−71 °C; 1H NMR (400 MHz, CDCl3): δ 7.87 (d, J = 8.4 Hz, 1H), 7.28 (t,
J = 8.0 Hz, 2H), 7.19−7.15 (m, 2H), 7.11 (t, J = 7.2 Hz, 1H), 6.85 (d, J = 8.0 Hz, 2H),
2.41 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 159.2, 142.1, 139.6, 129.9, 128.1, 127.2,
125.0, 119.8, 113.9, 107.6, 21.8; IR (thin film) 3419, 3055, 2969, 1726, 1480, 1375,
1270, 1069, 812, 754 cm−1; HRMS (ESI) m/z calcd for C13H12ON3 (M+H)+ 226.0980,
found 226.0972.
6-Chloro-1-phenoxy-1H-benzo[d][1,2,3]triazole (3da), white solid, 0.099 g, 81%
yield. mp: 76−77 °C; 1H NMR (500 MHz, CDCl3): δ 8.02 (d, J = 9.0 Hz, 1H), 7.54 (s,
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1H), 7.41−7.35 (m, 3H), 7.22 (t, J = 7.5 Hz, 1H), 6.95 (d, J = 8.0 Hz, 2H); 13C NMR
(125 MHz, CDCl3): δ 159.1, 142.0, 135.3, 130.1, 128.4, 126.3, 125.5, 121.5, 114.1,
108.5; IR (thin film) 3417, 3090, 2943, 1780, 1477, 1370, 1263, 1087, 822, 750 cm−1;
HRMS (ESI) m/z calcd for C12H9N3OCl (M+H)+ 246.0433, found 246.0439.
1-Phenoxy-6-(trifluoromethyl)-1H-benzo[d][1,2,3]triazole (3ea), white solid,
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1
0.103 g, 74% yield. mp: 105−106 °C; H NMR (500 MHz, CDCl3): δ 8.24 (d, J = 9.0
Hz, 1H), 7.87 (s, 1H), 7.69 (d, J = 9.0 Hz, 1H), 7.40 (t, J = 8.0 Hz, 2H), 7.24−7.21 (m,
1H), 6.98 (d, J = 8.5 Hz, 2H); 13C NMR (125 MHz, CDCl3): δ 159.1, 144.5, 131.4 (q,
J = 33.3 Hz), 130.2, 127.2, 125.7, 124.6 (q, J = 270.7 Hz), 121.8 (q, J = 2.7 Hz),
121.7, 114.2, 107.2 (q, J = 4.6 Hz); IR (thin film) 3433, 3102, 2956, 1747, 1486, 1310,
1166, 939, 754, 667 cm−1; HRMS (ESI) m/z calcd for C13H7N3F3O (M−H)− 278.0541,
found 278.0547.
1-Phenoxy-1H-benzo[d][1,2,3]triazole-6-carbonitrile (3fa), white solid, 0.073 g,
62% yield. mp: 122−123 °C; 1H NMR (400 MHz, CDCl3): δ 8.16 (d, J = 8.4 Hz, 1H),
7.88 (s, 1H), 7.60 (d, J = 8.8 Hz, 1H), 7.34−7.30 (m, 2H), 7.19 (d, J = 8.4 Hz, 1H),
6.91 (d, J = 8.0 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ 159.0, 144.3, 130.3, 127.7,
127.2, 125.9, 122.0, 117.7, 114.6, 114.2, 112.3; IR (thin film) 3417, 3099, 2978, 1721,
1484, 1375, 1275, 1068, 829, 749 cm−1; HRMS (ESI) m/z calcd for C13H7N4O
(M−H)− 235.0620, found 235.0625.
4-Chloro-1-phenoxy-1H-benzo[d][1,2,3]triazole (3ga), pale yellow solid, 0.062g,
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50% yield. mp: 67−68 °C; H NMR (400 MHz, CDCl3): δ 7.37 (s, 3H), 7.29 (t, J =
7.6 Hz, 2H), 7.18−7.12 (m, 1H), 6.86 (d, J = 8.0 Hz, 2H); 13C NMR (100 MHz,
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CDCl3): δ 159.1, 140.9, 130.0, 129.5, 129.1, 126.1, 125.5, 124.8, 114.0, 107.4; IR
(thin film) 3415, 3071, 2927, 1773, 1484, 1376, 1227, 1091, 778, 747 cm−1; HRMS
(ESI) m/z calcd for C12H9ON3Cl (M+H)+ 246.0434, found 246.0425.
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3-Phenoxy-3H-[1,2,3]triazolo[4,5-b]pyridine (3ha), white solid, 0.095 g, 90%
yield. mp: 84−85 °C; 1H NMR (500 MHz, CDCl3): δ 8.75 (d, J = 8.0 Hz, 1H), 8.45 (t,
J = 8.5 Hz, 1H), 7.46−7.44 (m, 1H), 7.37−7.34 (m, 2H), 7.22 (t, J = 7.5 Hz, 1H), 7.12
(d, J = 8.0 Hz, 2H); 13C NMR (125MHz, CDCl3): δ 159.4, 151.8, 140.0, 135.0, 129.9,
129.4, 125.6, 120.9, 115.1; IR (thin film) 3417, 3066, 2925, 1586, 1482, 1381, 1236,
1018, 775, 750 cm−1; HRMS (ESI) m/z calcd for C11H9N4O (M+H)+ 213.0776, found
213.0770.
1-Phenoxy-1H-[1,2,3]triazolo[4,5-b]pyridine (3ia), yellow solid, 0.064 g, 60%
yield. mp: 98−99 °C; 1H NMR (400 MHz, CDCl3): δ 8.86 (d, J = 3.6 Hz, 1H), 7.98 (d,
J = 7.6 Hz, 1H), 7.55−7.52 (m, 1H), 7.41 (t, J = 8.0 Hz, 2H), 7.26 (t, J = 7.6 Hz, 1H),
6.99 (d, J = 8.0 Hz, 2H); 13C NMR (100 MHz, CDCl3): δ 159.1, 154.1, 149.3, 130.1,
125.7, 123.4, 120.3, 117.9, 114.1; IR (thin film) 3432, 2344, 1583, 1482, 1383, 1269,
1153, 754, 684 cm−1; HRMS (ESI) m/z calcd for C11H9N4O (M+H)+ 213.0776, found
213.0767.
5-Methyl-1-phenoxy-1H-benzo[d][1,2,3]triazole (3ja), yellow solid, 0.041 g, 36%
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yield. mp: 92−93 °C; H NMR (400 MHz, CDCl3): δ 7.84−7.80 (m, 1H), 7.40−7.34
(m, 4H), 7.18−7.16 (m, 1H), 6.92−6.91 (m, 2H), 2.53 (s, 3H); 13C NMR (100 MHz,
CDCl3): δ 159.3, 144.1, 135.2, 130.8, 130.0, 126.2, 125.1, 119.3, 113.9, 108.2, 21.5;
IR (thin film) 3436, 2923, 1586, 1480, 1367, 1238, 1159, 1083, 802, 755 cm−1;
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HRMS (ESI) m/z calcd for C13H12N3O (M+H)+ 226.0980, found 226.0975.
5-Chloro-1-phenoxy-1H-benzo[d][1,2,3]triazole (3ka), yellow solid, 0.053 g, 43%
yield. mp: 77−78 °C; 1H NMR (400 MHz, CDCl3): δ 8.09 (s, 1H), 7.51−7.47 (m, 2H),
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7.37 (t, J = 7.0 Hz, 2H), 7.22 (t, J = 7.0 Hz, 1H), 6.94 (d, J = 7.0 Hz, 2H); C NMR
(100 MHz, CDCl3): δ 159.1, 144.0, 131.0, 130.1, 129.7, 126.5, 125.5, 119.8, 114.0,
109.7; IR (thin film) 3433, 2925, 1585, 1477, 1373, 1261, 1151, 799, 744 cm−1;
HRMS (ESI) m/z calcd for C12H9N3OCl (M+H)+ 246.0434, found 246.0430.
General procedure for synthesis of rearrangement products 4 from 3 (Table 4):
In a 25 mL Schlenk tube was charged with 3 (0.5 mmol) and MeCN (5 mL). The
reaction mixture was stirred vigorously at 60 °C for 18−24 h until the substrate 3
disappeared (monitored by TLC). At this time, the solvent was removed under
reduced pressure and the crude product was purified by flash chromatography (the
crude residue was dry loaded on silica gel; 1 / 10 − 1 / 1, ethyl acetate / petroleum
ether) to provide product 4 as solid.
2-(1H-Benzo[d][1,2,3]triazol-1-yl)phenol (4aa), white solid, 0.073 g, 70% yield.
mp: 205−206 °C; 1H NMR (500 MHz, DMSOꢀd6): δ 10.39 (s, 1H), 8.14 (d, J = 8.5 Hz,
1H), 7.58−7.55 (m, 1H), 7.50−7.44 (m, 4H), 7.18 (d, J = 7.0 Hz, 1H), 7.07−7.03 (m,
1H); 13C NMR (125 MHz, DMSOꢀd6): δ 152.4, 145.4, 134.0, 131.6, 128.5, 128.2,
124.5, 123.7, 120.0, 119.6, 117.5, 112.0; IR (thin film) 3424, 3074, 2966, 1601, 1463,
1277, 1099, 1011, 785, 742 cm−1; HRMS (ESI) m/z calcd for C12H8N3O (M−H)−
210.0667, found 210.0672.
2-(1H-Benzo[d][1,2,3]triazol-1-yl)-4-methylphenol (4ac), white solid, 0.059 g, 52%
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yield. mp: 196−197 °C; H NMR (400 MHz, DMSOꢀd6): δ 10.11 (brs, 1H), 8.14 (d, J
= 8.4 Hz, 1H), 7.58 (t, J = 7.6 Hz, 1H), 7.47−7.43 (m, 2H), 7.30−7.25 (m, 2H), 7.08
(d, J = 8.4 Hz, 1H), 2.30 (s, 3H); 13C NMR (100 MHz, DMSOꢀd6): δ 149.9, 145.4,
134.0, 132.0, 129.1, 129.1, 128.5, 128.2, 124.4, 123.3, 119.6, 117.3, 112.1, 20.2; IR
(thin film) 3668, 3426, 2977, 1617, 1395, 1247, 1062, 888, 734 cm−1; HRMS (ESI)
m/z calcd for C13H11N3ONa (M+Na)+ 248.0800, found 248.0791.
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2-(1H-Benzo[d][1,2,3]triazol-1-yl)-4,6-dimethylphenol (4af), white solid, 0.085 g,
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71% yield. mp: 85−86 °C; H NMR (400 MHz, CDCl3): δ 7.76 (d, J = 8.4 Hz, 1H),
7.40 (t, J = 8.0 Hz, 1H), 7.26−7.22 (m, 2H), 6.80 (s, 1H), 6.69 (s, 1H), 2.31 (s, 3H),
1.79 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 152.2, 145.1, 141.7, 136.5, 133.9, 128.1,
124.4, 123.5, 119.8, 119.4, 115.8, 110.2, 21.4, 17.4; IR (thin film) 3098, 2922, 1597,
1452, 1320, 1273, 1106, 1055, 839, 746 cm−1; HRMS (ESI) m/z calcd for C14H14N3O
(M+H)+ 240.1137, found 240.1129.
2-(1H-Benzo[d][1,2,3]triazol-1-yl)-5-nitrophenol (4ag), white solid, 0.073 g, 57%
yield. mp: 241−242 °C; 1H NMR (400 MHz, DMSOꢀd6): δ 11.49 (s, 1H), 8.19 (d, J =
8.4 Hz, 1H), 7.75−7.68 (m, 2H), 7.64 (t, J = 7.6 Hz, 1H), 7.57 (s, 1H), 7.55−7.48 (m,
2H); 13C NMR (100 MHz, DMSOꢀd6): δ 155.0, 147.6, 145.3, 134.3, 132.4, 129.0,
124.9, 122.6, 119.9, 116.0, 115.7, 111.5; IR (thin film) 3666, 3405, 2978, 1611, 1532,
1366, 1254, 1066, 811, 741 cm−1; HRMS (ESI) m/z calcd for C12H9N4O3 (M+H)+
257.0675, found 257.0665.
2-(1H-Benzo[d][1,2,3]triazol-1-yl)-6-methylphenol (4ah), white solid, 0.064 g, 57%
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yield. mp: 179−180 °C; H NMR (400 MHz, DMSOꢀd6): δ 9.23 (s, 1H), 8.15 (d, J =
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8.5 Hz, 1H), 7.57−7.54 (m, 1H), 7.47−7.44 (m, 2H), 7.38 (d, J = 7.5 Hz, 1H), 7.28 (d,
J = 7.5 Hz, 1H), 7.00 (d, J = 7.5 Hz, 1H), 2.32 (s, 3H); 13C NMR (100 MHz,
DMSOꢀd6): δ 150.4, 145.5, 134.2, 132.6, 128.2, 127.8, 125.9, 124.6, 124.4, 120.2,
119.7, 111.8, 17.0; IR (thin film) 3417, 2975, 2693, 1592, 1478, 1357, 1219, 1065,
785, 738 cm−1; HRMS (ESI) m/z calcd for C13H12N3O (M+H)+ 226.0980, found
226.0972.
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2-(1H-Benzo[d][1,2,3]triazol-1-yl)-4-bromophenol (4aj), white solid, 0.082 g, 57%
yield. mp: 227−229 °C; 1H NMR (400 MHz, DMSOꢀd6): δ 10.76 (s, 1H), 8.16 (d, J =
8.4 Hz, 1H), 7.76 (d, J = 2.4 Hz, 1H), 7.66−7.63 (m, 1H), 7.58 (d, J = 6.8 Hz, 1H),
7.52−7.47 (m, 2H), 7.15 (d, J = 8.8 Hz, 1H); 13C NMR (100 MHz, DMSOꢀd6): δ
152.0, 145.4, 134.2, 133.9, 130.8, 128.5, 125.0, 124.6, 119.7, 119.4, 112.0, 110.2; IR
(thin film) 3660, 3080, 2964, 1721, 1593, 1498, 1393, 1280，1075，742 cm−1; HRMS
(ESI) m/z calcd for C12H8N3OBrNa (M+Na)+ 311.9748, found 311.9732.
Methyl 3-(1H-benzo[d][1,2,3]triazol-1-yl)-4-hydroxybenzoate (4am), white solid
0.115 g, 86% yield. mp: 241−242 °C; 1H NMR (400 MHz, DMSOꢀd6): δ 11.47 (s, 1H),
8.17 (d, J = 8.0 Hz, 1H), 8.08−8.06 (m, 2H), 7.61−7.57 (m, 1H), 7.53−7.46 (m, 2H),
7.30 (t, J = 8.4 Hz, 1H), 3.84 (s, 3H); 13C NMR (100 MHz, DMSOꢀd6): δ 165.7, 156.8,
145.4, 133.9, 132.8, 129.8, 128.5, 124.7, 123.8, 121.5, 119.8, 117.7, 112.0, 52.5; IR
(thin film) 3422, 2975, 2615, 1725, 1610, 1432, 1278, 1050, 881, 754 cm−1; HRMS
(ESI) m/z calcd for C14H12N3O3 (M+H)+ 270.0879, found 270.0870.
2-(1H-[1,2,3]Triazolo[4,5-b]pyridin-1-yl)phenol (4ha), white solid, 0.065 g, 61%
yield. mp: 220−221 °C; 1H NMR (400 MHz, DMSOꢀd6): δ 10.52 (s, 1H), 8.78 (d, J =
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3.6 Hz, 1H), 8.08 (d, J = 8.4 Hz, 1H), 7.64 (dd, J = 8.4 Hz, 4.0 Hz, 1H), 7.58 (d, J =
7.6 Hz, 1H), 7.50 (t, J = 7.6 Hz, 1H), 7.20 (d, J = 8.0 Hz, 1H), 7.09 (d, J = 7.6 Hz,
1H); 13C NMR (100 MHz, DMSOꢀd6): δ 157.0, 152.0, 148.7, 131.8, 128.2, 126.5,
123.6, 123.4, 121.7, 120.2, 117.5; IR (thin film) 3409, 3097, 2967, 2735, 1598, 1516,
1464, 1280, 1094, 1005, 785, 749 cm−1; HRMS (ESI) m/z calcd for C11H9N4O
(M+H)+ 213.0776, found 213.0768.
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2-(5-Methoxy-1H-benzo[d][1,2,3]triazol-1-yl)phenol (4ba), white solid, 0.102 g,
85% yield. mp: 190−191 °C; (Major isomer) 1H NMR (400 MHz, DMSOꢀd6): δ 10.35
(s, 1H), 8.00 (d, J = 8.8 Hz, 1H), 7.54 (d, J = 1.6 Hz, 1H), 7.48−7.42 (m, 2H), 7.37 (d,
J = 8.8 Hz, 1H), 7.20−7.15 (m, 1H), 7.06−7.02 (m, 1H), 3.87 (s, 3H); 13C NMR (100
MHz, DMSOꢀd6): δ 157.2, 152.1, 146.4, 140.6, 131.4, 128.3, 123.8, 120.3, 120.0,
117.5, 112.7, 92.1, 56.2; (Minor isomer) 1H NMR (400 MHz, DMSOꢀd6): δ 10.35 (s,
1H), 7.48−7.42 (m, 2H), 7.48 (s, 1H), 7.20−7.15 (m, 2H), 7.06−7.02 (m, 1H), 6.78 (d,
J = 1.6 Hz, 1H), 3.79 (s, 3H); 13C NMR (100 MHz, DMSOꢀd6): δ 160.1, 152.4, 146.4,
135.3, 129.5, 128.4, 123.8, 120.4, 120.0, 117.6, 116.6, 98.9, 56.2; IR (thin film) 3442,
2378, 1607, 1518, 1453, 1383, 1274, 1213, 1035, 784, 737 cm−1; HRMS (ESI) m/z
calcd for C13H12N3O2 (M+H)+ 242.0930, found 242.0920.
2-(5-Chloro-1H-benzo[d][1,2,3]triazol-1-yl)phenol (4da), white solid, 0.109 g, 89%
yield. mp: 218−219 °C; 1H NMR (400 MHz, DMSOꢀd6): δ 10.47 (s, 1H), 8.30 (s, 1H),
7.61−7.58 (m, 1H), 7.53−7.46 (m, 3H), 7.19 (d, J = 8.4 Hz, 1H), 7.08 (t, J = 7.6 Hz,
1H); 13C NMR (100 MHz, DMSOꢀd6): δ 152.2, 146.0, 132.9, 131.8, 129.1, 128.8,
128.4, 123.3, 120.1, 119.0, 117.5, 113.8; IR (thin film) 3434, 3083, 2972, 2738, 1601,
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1464, 1276, 1122, 936, 802, 740 cm−1; HRMS (ESI) m/z calcd for C12H9N3OCl
(M+H)+ 246.0434, found 246.0424.
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0.112 g, 81% yield. mp: 223−224 °C; H NMR (500 MHz, DMSOꢀd6): δ 10.54 (s,
1H), 8.68 (s, 1H), 7.89 (d, J = 8.5 Hz, 1H), 7.73 (d, J = 8.5 Hz, 1H), 7.57 (d, J = 8.0
Hz, 1H), 7.52 (t, J = 7.5 Hz, 1H), 7.21 (d, J = 8.5 Hz, 1H), 7.10 (d, J = 7.5 Hz, 1H);
13C NMR (125 MHz, DMSOꢀd6): δ 152.3, 144.6, 135.6, 132.0, 128.5, 125.8 (q, J =
270.7 Hz), 125.3 (q, J = 31.8 Hz), 124.7 (q, J = 2.8 Hz), 123.1, 120.2, 118.3 (q, J =
4.6 Hz), 117.5, 113.8; IR (thin film) 3432, 3086, 2962, 2736, 1599, 1463, 1333, 1221,
1133, 825, 754 cm−1; HRMS (ESI) m/z calcd for C13H9N3OF3 (M+H)+ 280.0698,
found 280.0689.
2-(6-Methyl-1H-benzo[d][1,2,3]triazol-1-yl)phenol (4ja), yellowish solid, 0.071g,
63% yield. mp: 189−190 °C; 1H NMR (500 MHz, DMSOꢀd6): δ 10.36 (s, 1H), 8.00 (d,
J = 8.0 Hz, 1H), 7.47−744 (m, 2H), 7.28 (d, J = 8.5 Hz, 1H), 7.24 (s, 1H), 7.18 (d, J =
8.5 Hz, 1H), 7.06 (t, J = 7.5 Hz, 1H), 2.46 (s, 3H); 13C NMR (125 MHz, DMSOꢀd6): δ
152.5, 144.0, 138.4, 134.5, 131.5, 128.5, 126.6, 123.8, 120.0, 119.2, 117.5, 110.9,
21.8; IR (thin film) 3386, 3066, 2927, 2724, 1601, 1513, 1458, 1276, 1111,797, 741
cm−1; HRMS (ESI) m/z calcd for C13H12N3O (M+H)+ 226.0980, found 226.0974.
2-(6-Chloro-1H-benzo[d][1,2,3]triazol-1-yl)phenol (4ka), yellowish solid, 0.052 g,
43% yield. mp: 215−216 °C; 1H NMR (400 MHz, DMSOꢀd6): δ 10.46 (s, 1H), 8.20 (d,
J = 8.8 Hz, 1H), 7.57 (s, 1H), 7.53−7.45 (m, 3H), 7.19 (d, J = 8.0 Hz, 1H), 7.08 (t, J =
7.8 Hz, 1H); 13C NMR (100 MHz, DMSOꢀd6): δ 152.1, 144.1, 134.5, 133.2, 131.7,
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128.3, 125.3, 123.3, 121.3, 120.1, 117.6, 111.8; IR (thin film) 3429, 3072, 2926, 2734,
1603, 1515, 1463, 1272, 1101, 803, 744 cm−1; HRMS (ESI) m/z calcd for
C12H9N3OCl (M+H)+ 246.0434, found 246.0431.
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General procedure for one-pot reaction for synthesis of rearrangement
products 4 (Table 5): In a 25 mL Schlenk tube was charged with 1 (0.5 mmol) and
MeCN (5 mL). tꢀBuOK (0.75 mmol, 1.5 equiv) was added in one portion at room
temperature. The mixture was stirred vigorously at room temperature for 5 min. Then,
diaryliodonium salts 2 (0.75 mmol, 1.5 equiv) was added in one portion. The reaction
mixture was stirred vigorously at 60 °C for 18−24 h until the substrate 1 disappeared
(monitored by TLC). At this time, the solvent was removed under reduced pressure
and the crude product was purified by flash chromatography (the crude residue was
dry loaded on silica gel; 1 / 10 − 1 / 2, ethyl acetate / petroleum ether) to provide
product 4 as solid.
2-(1H-Benzo[d][1,2,3]triazol-1-yl)-4-methoxyphenol (4ab), yellow solid, 0.095 g,
79% yield. mp: 163−164 °C; 1H NMR (400 MHz, DMSOꢀd6): δ 9.84 (s, 1H), 8.16 (d,
J = 8.0 Hz, 1H), 7.59 (t, J = 7.6 Hz, 1H), 7.50−7.43 (m, 2H), 7.11−7.08 (m, 3H), 3.74
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(s, 3H); C NMR (100 MHz, DMSOꢀd6): δ 152.7, 146.0, 145.3, 133.9, 128.2, 124.5,
123.7, 119.6, 118.2, 117.7, 113.0, 112.1, 56.2; IR (thin film) 3442, 2378, 1607, 1518,
1453, 1383, 1274, 1213, 1035, 784, 737 cm−1; HRMS (ESI) m/z calcd for C13H12N3O2
(M+H)+ 242.0930, found 242.0922.
2-(1H-Benzo[d][1,2,3]triazol-1-yl)-4-tert-butylphenol (4an), yellowish solid, 0.109
g, 82% yield. mp: 156−157 °C; 1H NMR (400 MHz, DMSOꢀd6): δ 10.18 (s, 1H), 8.15
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(d, J = 8.0 Hz, 1H), 7.58−7.45 (m, 5H), 7.14 (d, J = 8.8 Hz, 1H), 1.30 (s, 9H); 13C
NMR (100 MHz, DMSOꢀd6): δ 149.8, 145.4, 142.6, 134.0, 128.3, 128.1, 124.8, 124.4,
123.1, 119.6, 117.1, 112.2, 34.3, 31.6; IR (thin film) 3042, 2962, 2783, 2621, 1739,
1609, 1512, 1265, 1109, 830, 738 cm−1; HRMS (ESI) m/z calcd for C16H18N3O
(M+H)+ 268.1450, found 268.1441.
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4-Methoxy-2-(5-methyl-1H-benzo[d][1,2,3]triazol-1-yl)phenol (4cb), white solid,
0.108 g, 85% yield. mp: 164−165 °C; (major isomer) 1H NMR (400 MHz, DMSOꢀd6):
δ 9.83 (s, 1H), 7.89 (s, 1H), 7.39 (s, 2H), 7.10ꢀ7.05 (m, 3H), 3.74 (s, 3H), 2.49 (s, 3H);
13C NMR (100 MHz, DMSOꢀd6): δ 152.7, 145.9, 145.8, 134.0, 132.5, 130.5, 130.2,
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123.9, 118.2, 117.5, 112.9, 111.8, 56.2, 21.4; (minor isomer) H NMR (400 MHz,
DMSOꢀd6): δ 9.80 (s, 1H), 8.00 (d, J = 7.2 Hz, 1H), 7.29ꢀ7.26 (m, 2H), 7.10ꢀ7.05 (m,
3H), 3.75 (s, 3H), 2.47 (s, 3H); 13C NMR (100 MHz, DMSOꢀd6): δ 152.7, 146.1,
144.0, 138.4, 134.4, 126.6, 123.8, 119.1, 118.3, 117.6, 113.1, 111.0, 56.2, 21.8; IR
(thin film) 3431, 2962, 2767, 1604, 1516, 1460, 1280, 1210, 1040, 887, 786 cm−1;
HRMS (ESI) m/z calcd for C14H13N3O2Na (M+Na)+ 278.0905, found 278.0894.
2-(5-Chloro-1H-benzo[d][1,2,3]triazol-1-yl)-4-methoxyphenol (4db), white solid,
0.088 g, 64% yield. mp: 209−210 °C; (major isomer) 1H NMR (400 MHz, DMSOꢀd6):
δ 9.95 (s, 1H), 8.30 (s, 1H),7.59 (s, 1H), 7.55 (d, J = 9.0 Hz, 1H), 7.13−7.12 (m, 1H),
7.10−7.08 (s, 2H), 3.75 (s, 3H); 13C NMR (100 MHz, DMSOꢀd6): δ 152.7, 145.8,
145.7, 132.8, 128.8, 125.4, 123.3, 119.0, 118.3, 118.0, 113.9, 112.9, 56.2; (minor
isomer) 1H NMR (400 MHz, DMSOꢀd6): δ 9.95 (s, 1H), 8.20 (d, J = 9.0 Hz, 1H), 7.61
(s, 1H), 7.51 (dd, J = 9.0 Hz, 1.0 Hz, 1H), 7.13−7.12 (m, 1H), 7.10−7.08 (s, 2H), 3.75
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(s, 3H); C NMR (100 MHz, DMSOꢀd6): δ 152.8, 146.0, 144.1, 133.3, 129.1, 125.4,
123.3, 121.3, 118.3, 118.0, 113.9, 111.9, 56.2; IR (thin film) 3010, 2771, 1609, 1517,
1467, 1272, 1212, 1038, 804 cm−1; HRMS (ESI) m/z calcd for C13H11N3O2Cl (M+H)+
276.0540, found 276.0531.
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1-(2-Hydroxy-5-methoxyphenyl)-1H-benzo[d][1,2,3]triazole-5-carbonitrile (4fb),
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yellowish solid, 0.066 g, 50% yield. mp: 237−239 °C; (one isomer) H NMR (400
MHz, DMSOꢀd6): δ 9.98 (s, 1H), 8.38 (d, J = 8.4 Hz, 1H), 8.20 (s, 1H), 7.93 (d, J =
8.8 Hz, 1H), 7.17 (s, 1H), 7.11 (s, 2H), 3.76 (s, 3H); 13C NMR (100 MHz, DMSOꢀd6):
δ 152.7, 145.9, 145.8, 135.6, 130.6, 127.0, 121.4, 118.7, 118.4, 118.3, 114.0, 112.9,
107.2, 56.2; (the other isomer) 1H NMR (400 MHz, DMSOꢀd6): δ 9.99 (s, 1H), 8.70 (s,
1H), 8.09 (d, J = 8.0 Hz, 1H), 7.84−7.82 (m, 1H), 7.69 (d, J = 8.4 Hz, 1H), 7.17 (s,
2H), 3.75 (s, 3H); 13C NMR (100 MHz, DMSOꢀd6): δ 152.7, 146.6, 144.6, 135.6,
133.3, 126.5, 123.0, 122.9, 119.2, 118.9, 118.7, 112.9, 110.6, 56.2; IR (thin film) 3663,
3413, 2977, 2228, 1608, 1515, 1392, 1212, 1050, 886, 815 cm−1; HRMS (ESI) m/z
calcd for C14H11N4O2 (M+H)+ 267.0882, found 267.0873.
General procedure for synthesis of 5: In a 25 mL Schlenk tube was charged with
4aa (0.5 mmol) and MeCN (5 mL). tꢀBuOK (0.75 mmol, 1.5 equiv) was added in one
portion at room temperature. The mixture was stirred vigorously at room temperature
for 5 min. Then, diaryliodonium salts 2l (0.75 mmol, 1.5 equiv) was added in one
portion. The reaction mixture was stirred vigorously at room temperature for 18 h
until the substrate 4aa disappeared (monitored by TLC). At this time, the solvent was
removed under reduced pressure and the crude product was purified by flash
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chromatography (the crude residue was dry loaded on silica gel; 1 / 20 − 1 / 5, ethyl
acetate / petroleum ether) to provide product 5 as solid.
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1-(2-(2-Bromophenoxy)phenyl)-1H-benzo[d][1,2,3]triazole (5), light yellow oil,
0.151 g, 83% yield. 1H NMR (400 MHz, CDCl3): δ 7.99 (d, J = 8.4 Hz, 1H), 7.65 (d,
J = 8.4 Hz, 1H), 7.58 (d, J = 7.6 Hz, 1H), 7.42−7.35 (m, 3H), 7.30 (t, J = 8.0 Hz, 1H),
7.23−7.19 (m, 1H), 7.10 (t, J = 7.6 Hz, 1H), 6.87−6.81 (m, 3H); 13C NMR (100 MHz,
CDCl3): δ 152.0, 150.7, 145.5, 133.9, 133.7, 130.8, 128.7, 128.5, 127.7, 126.8, 125.8,
123.9, 123.8, 120.7, 119.6, 118.0, 114.7, 111.5; IR (thin film) 3065, 2856, 1586, 1460,
1252, 1116, 1049, 749 cm−1; HRMS (ESI) m/z calcd for C18H13N3OBr (M+H)+
366.0242, found 366.0220.
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General procedure for synthesis of 6: In a 25 mL Schlenk tube was charged with
5 (0.5 mmol) and THF (5 mL) under N2 atmosphere. The mixture was stirred
vigorously at −78 °C for 2 min. nꢀBuLi (0.75 mmol, 1.6 M in hexane, 1.5 equiv) was
added slowly. After completion, the mixture was kept at −78 °C for 1 h. Then, PPh2Cl
(0.5 mmol, 1.0 equiv) was dropped to the mixture slowly. The reaction mixture was
stirred vigorously for 2 h and then moved to room temperature for 1 h until 5 was
disappeared (monitored by TLC). At this time, quenched by water (10 mL) and
exacted with ether (3 × 10 mL). The organic layers were combined, washed with brine
(10 mL), dried over Na2SO4, and filtered. Then, the solvent was removed under
reduced pressure and the crude product was purified by flash chromatography (the
crude residue was dry loaded on silica gel; 1 / 50 − 1 / 10, ethyl acetate / petroleum
ether) to provide product 6 as solid.
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1-(2-(2-(Diphenylphosphino)phenoxy)phenyl)-1H-benzo[d][1,2,3]triazole
(6),
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white solid, 0.094 g, 40% yield. mp: 187−188 °C; H NMR (500 MHz, CDCl3): δ
7.99 (d, J = 8.0 Hz, 1H), 7.58 (d, J = 8.0 Hz, 1H), 7.48 (d, J = 8.5 Hz, 1H), 7.39 (d, J
= 7.5 Hz, 1H), 7.28−7.21 (m, 5H), 7.18−7.15 (m, 5H), 7.12 (t, J = 7.5 Hz, 4H), 7.02 (t,
J = 7.5 Hz, 1H), 6.93−6.90 (m, 2H), 6.80−6.78 (m, 1H); 13C NMR (125 MHz, CDCl3):
δ 157.9, 157.8, 151.3, 145.4, 135.8 (d, JCꢀP = 10.0 Hz), 134.3, 133.8, 133.6, 133.5,
133.4, 133.3, 130.6 (d, JCꢀP = 4.8 Hz), 129.6 (d, JCꢀP = 4.0 Hz), 128.5, 128.4, 128.3,
128.2, 127.5, 127.2, 124.7, 123.7, 123.6, 119.4, 119.0, 118.7, 111.4 (d, JCꢀP = 2.7 Hz);
IR (thin film) 3447, 3061, 1586, 1502, 1435, 1242, 1080, 748, 696 cm−1; HRMS (ESI)
m/z calcd for C30H23N3OP (M+H)+ 472.1579, found 472.1606.
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General procedure for Synthesis of N-hydroxybenzotriazoles 1: In a 100 mL
roundꢀbottle flask was charged with oꢀchloronitrobenzene derivatives (11.655 mmol)
and EtOH (40 mL). Then, hydrazine hydrate (116.6 mmol, 10 equiv) was added at
room temperature. The mixture was stirred vigorously under refluxing for 20 h and
then cooled to room temperature. EtOH was evaporated under reduced pressure from
the reaction mixture. Cold MeOH (20 mL) was added to the residue and the mixture
was acidified with conc. HCl. This addition induced precipitation of a solid. The solid
was collected by filtration and washed with amount of cold MeOH to provide
Nꢀhydroxy benzotriazoles 1 as solid.
Nꢀhydroxy benzotriazole 1a, 1d, 1e, 1h, 1j and 1k were purchased from
SigmaꢀAldrich. 1b,14 1c, 8a 1f, 8a 1g15 and 1i16 were prepared as the literatures, and
spectra data matched literature values.
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