Tandem C-O and C-N Bonds Formation Through O-Arylation and [3,3]-Rearrangement by Diaryliodonium Salts: Synthesis of N-Aryl Benzo[1,2,3]triazin-4(1H)-one Derivatives

Article abstract of DOI:10.1021/acs.joc.5b01947

Metal-free O-arylation and [3, 3]-rearrangement have been shown as an efficient strategy to construct new C-O and C-N bonds in one-pot reactions. The method was used to prepare N-aryl benzo[1,2,3]triazin-4(1H)-one derivatives in good yields from N-hydroxy benzo[1,2,3]triazin-4(3H)-one and diaryliodonium salts. The reaction was tolerated a variety of sensitive functional groups such as iodine, nitro, ester, and aldehyde groups. A rational mechanism was proposed based on the experimental results, and the reaction was easily up to gram scale.

Full text of DOI:10.1021/acs.joc.5b01947

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Note
Tandem C-O and C-N bonds Formation Through O-
Arylation and [3,3]-Rearrangement by Diaryliodonium Salts:
Synthesis of N-Aryl Benzo[1,2,3]triazin-4(1H)-one Derivatives
Wei-Min Shi, Xiao-Pan Ma, Cheng-Xue Pan, Gui-Fa Su, and Dong-Liang Mo
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.5b01947 • Publication Date (Web): 16 Oct 2015
Downloaded from http://pubs.acs.org on October 19, 2015
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Tandem C−O and C−N bonds Formation Through O-Arylation
and [3,3]-Rearrangement by Diaryliodonium Salts: Synthesis
of N-Aryl Benzo[1,2,3]triazin-4(1H)-one Derivatives
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WeiꢀMin Shi, XiaoꢀPan Ma, ChengꢀXue Pan, GuiꢀFa Su*, and DongꢀLiang Mo*
Key Laboratory for the Chemistry and Molecular Engineering of Medicinal Resources,
Ministry of Education of China; School of Chemistry & Pharmaceutical Sciences,
Guangxi Normal University, 15 Yu Cai Road, Guilin 541004, China.
O
N
N
O
N
R1
R
OH
I
OTf
tꢀBuOK
N
N
N
+
R
DCE, 80 °C
OH
R2
R1
New CꢀO and CꢀN bonds
23 examples
35 ꢀ 88% yields
ABSTRACT: Metalꢀfree Oꢀarylation and [3, 3]ꢀrearrangement have been showed as
an efficient strategy to construct new C−O and C−N bonds in oneꢀpot reaction. The
method was used to prepare Nꢀaryl benzo[1,2,3]triazinꢀ4(1H)ꢀone derivatives in good
yields from Nꢀhydroxy benzo[1,2,3]triazinꢀ4(3H)ꢀone and diaryliodonium salts. The
reaction was tolerated a variety of sensitive functional groups such as iodine, nitro,
ester, and aldehyde groups. A rational mechanism was proposed based on the
experimental results and the reaction was easily up to gram scale.
[3,3]ꢀRearrangement reactions, as features in the chemistry field which could build
surprising and unexpected structures, have attracted much attentions for chemists.1
Many compounds that are difficult to synthesize by traditional methods could be
obtained easily by [3,3]ꢀrearrangement.2 The rearrangement of N−O bond compounds
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was one of the most important strategies to construct C−C or C−heteroatom bonds in
organic synthesis due to its efficient access to diverse scaffolds,3 such as
2ꢀaminoꢀ2’ꢀhydroxyꢀ1,1’ꢀbiaryl derivatives,4 polysubstituted furans,5 pyrroles,6
isoxazolines,7 or related functional compounds.8 In recent years, arylation of N−O
bond combined with [3,3]ꢀrearrangement have been demonstrated useful strategy in
organic synthesis because its fast construction of complex molecules.9 In 2010,
Buchwald developed a Pdꢀcatalyzed Oꢀarylation of ethyl acetohydroximate with aryl
chlorides, bromides, and iodides to prepare Oꢀarylhydroxyamines and further
condensation with ketones to construct benzofurans by [3,3]ꢀrearrangement (Scheme
1A).9a To overcome the shortcomings by transition metal catalysis, such as harsh
conditions, requirement of complicated ligands, and tolerance of sensitive functional
groups, the metalꢀfree strategy has been paid much attentions in the arylation
process.10, 11 Diaryliodonium salts have been utilized extensively as versatile arylation
agents for a variety of nucleophiles in transitionꢀmetal free conditions due to its easy
preparation, high reactivity and selectivity.12, 13 Very recently, Kürti and Olofsson
independently developed metalꢀfree Oꢀarylation of oximes by diaryliodonium salts as
accesses to Oꢀarylhydroxylamines and synthesis of benzofuran scaffolds via further
sequence of [3,3]ꢀrearrangement (Scheme 1B).11 Although the metalꢀfree Oꢀarylation
of N−O bond to proceed [3,3]ꢀrearrangement have been studied, as we known, only
new C−O and C−C bond was formed in the process. We envisioned that Oꢀarylation
of Nꢀhydroxybenzo[1,2,3]triazinꢀ4(3H)ꢀone with diaryliodonium salts and sequence
of [3,3]ꢀrearrangement on the Nꢀatom would produce new C−O and C−N bonds in
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oneꢀpot reaction and provide the Nꢀaryl benzo[1,2,3]triazinꢀ4(1H)ꢀone easily (Scheme
1C).14
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Benzo[1,2,3]triazinꢀ4ꢀone derivatives are not only as important heterocyclic
scaffolds in pharmaceutical and medicinal chemistry,15 but also served as important
organic intermediate.16 However, Nꢀaryl benzo[1,2,3]triazinꢀ4(1H)ꢀone derivatives
were rarely studied before due to its synthetic challenge.17 Herein, we report a simple
and mild method to construct C−O/C−N bonds in oneꢀpot reaction of Oꢀarylation and
[3,3]ꢀrearrangement. It would allow more facile to study the reactivities and
applications of these compounds.
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A) Pdꢀcatalyzed Oꢀarylation and [3,3]ꢀrearrangement to form CꢀO/CꢀC bonds
OH
O
Ar
N
[Pd]/Ligand
ArX
N
1) HCl
R
O
2)
EtO
O
EtO
R = aryl, alkyl
R
B) Metalꢀfree Oꢀarylation and [3,3]ꢀrearrangement to form CꢀO/CꢀC bonds
OH
O
Ar
HCl
N
N
base
Ar2IX
R1
R
+
R
O
R
R = OEt, Aryl
C) This work, metal free Oꢀarylation and [3,3]ꢀrearrangement to form CꢀO/CꢀN bonds
O
N
O
O
N
R
N
3
4
OH
O
Ar
N
Ar2IOTf
N
[3,3]
N
N
R
R
OH
N
2
N
1
R1
Scheme 1. Strategies of Oꢀarylation and [3,3]ꢀrearrangement process.
Initially, we ran the reaction of Nꢀhydroxybenzo[1,2,3]triazinꢀ4(3H)ꢀone 1a and
diphenyliodonium triflate 2a with tꢀBuOK in DMSO at 80 ˚C for 18 h. To our surprise,
no Oꢀarylation product was observed and only Nꢀaryl benzo[1,2,3]triazinꢀ4(1H)ꢀone
3a was observed in 38% yield (Table 1, entry 1). From product 3a, it showed that new
CꢀO bond and CꢀN bond were formed in the process. This observation inspired us to
develop an efficient method to construct new C−O and C−N bond to prepare Nꢀaryl
benzo[1,2,3]triazinꢀ4(1H)ꢀone. As illustrated in Table 1, the screening of solvents
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showed that DCE (1, 2ꢀdichloroethane) was the best solvent for this transformation
(Table 1, entries 1ꢀ8). The choice of base had great effect on the reaction (Table 1,
entries 8ꢀ12). Interestingly, product 3a was obtained in high yield with pyridine (Table
1, entry 13). The yield of product 3a decreased obviously either the temperature was
lower or higher (Table 1, entry 8 vs entries 14ꢀ17). No desired product 3a was
observed and only substrate 1a was recovered in the absence of base (Table 1, entry
18). Product 3a was very stable and not discomposed even at 140 ˚C for 24 h.18
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Table 1. Optimization of reaction a
O
O
N
N
N
OH
Conditions
N
N
+
Ph2IOTf
N
OH
1a
entry
2a
3a
base
solvent
T (˚C)
80
3a %b
38
56
76
27
59
78
75
88
26
82
55
50
85
0c
1
tꢀBuOK
tꢀBuOK
tꢀBuOK
tꢀBuOK
tꢀBuOK
tꢀBuOK
tꢀBuOK
tꢀBuOK
tꢀBuONa
NaH
DMSO
DMF
MeCN
MeOH
THF
2
80
3
80
4
80
5
80
6
Dioxane
Toluene
DCE
80
7
80
8
80
9
DCE
80
10
11
12
13
14
15
16
17
DCE
80
KOH
DCE
80
Cs2CO3
Pyridine
tꢀBuOK
tꢀBuOK
tꢀBuOK
tꢀBuOK
DCE
80
DCE
80
DCE
25
DCE
50
20
71
67
DCE
100
120
DCE
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18
ꢀ
DCE
80
0
4
a Reaction conditions: 1a (0.5 mmol), Ph2IOTf (0.75 mmol, 1.5 equiv), base (0.75
5
6
7
8
b
c
mmol, 1.5 equiv), solvent (5 mL), 18ꢀ24 h; Isolated yield; Oꢀarylation product 4a
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was isolated in 25% yield.
To examine the scope of present protocols, a variety of diaryliodonium salts 2
were subjected to the optimal conditions. As shown in Table 2, a series of desired
product 3 were obtained from moderate to good yields. This method was suitable for
both electronꢀrich and electronꢀdeficient diaryliodonium salts 2, either paraꢀ, metaꢀ,
or orthoꢀsubstituents on the iodonium salts. However, the metaꢀ, or orthoꢀsubstituted
diaryliodonium salts gave lower yields (Table 2, entries 7, 8 and 14) might due to the
steric hindrance. To our delight, the regioselectivity of product 3g and 3m was high
with only one isomer when the metaꢀsubstituted diaryliodonium salts 2g and 2m were
used (Table 2, entries 7 and 14). When unsymmetric diaryliodonium salts were used,
the reaction proceeded with high chemoselectivity and the more electronꢀdeficient
aryl moieties could be transferred to the desired products (Table 2, entries 9ꢀ16).19
However, when the aryl moieties was presented with electronꢀwithdrawing group, the
reaction needed to run at 100 ˚C in order to get high yields (Table 2, entries, 7, 15 and
16). In particular, for diaryliodonium salt 2i, the 4ꢀPhO substituted aryl group was
transferred to product 3i as major isomer and 4ꢀMeO substituted aryl moiety product
3b was isolated in 10% yield only (Table 2, entry 10). This method was compatible
with some important functional groups on the phenyl ring of the diaryliodonium salts,
such as fluorine, chlorine, bromine, methoxy, nitro, ester, and aldehyde substituents,
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which could be applied to further synthetic transformations easily.
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Table 2. The Scope of diaryliodonium salts.a
O
8
9
O
R1
N
OH
tꢀBuOK
N
I
OTf
N
N
+
10
11
12
13
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N
DCE, 80 °C
OH
N
R2
R1
1a
2
3
entry
1
2
2a
2b
2c
2d
2e
2f
R1
H
R2
3
yield%b
H
3a
3b
3c
3d
3e
3f
88
2
4ꢀMeO
4ꢀMe
4ꢀtꢀBu
4ꢀCl
4ꢀMeO
4ꢀMe
4ꢀtꢀBu
4ꢀCl
84
3
86
4
78
5
85
6
4ꢀF
4ꢀF
85
59c,d
7
2g
2h
2aa
2i
3ꢀNO2
2ꢀMe
H
3ꢀNO2
2ꢀMe
4ꢀMeO
4ꢀMeO
4ꢀMeO
4ꢀMeO
4ꢀMeO
4ꢀMeO
H
3g
3h
3a
3i
8
42
9
78
75e
10
11
12
13
14
15
16
4ꢀPhO
4ꢀPh
4ꢀiꢀPr
4ꢀBr
2j
3j
85
3k
3l
3k
3l
78
68
3m
3n
3o
3ꢀBr
3m
3n
3o
63c
74d
46d
4ꢀCO2Me
4ꢀCHO
H
a
Reaction conditions: 1a (0.5 mmol), iodonium salts 2 (0.75 mmol, 1.5 equiv),
b
c
tꢀBuOK (0.75 mmol, 1.5 equiv), DCE (5 mL), 80 ˚C, 18ꢀ24 h; Isolated yield;
regioselectivity for [3,3]ꢀrearrangement step, > 20:1, only one isomer; d ran at 100 ˚C;
e Product 3b was also isolated in 10% yield.
When substrate 1a reacted with diaryliodonium salts 2p, only <5% yield of
product 3p was observed perhaps due to steric hindrance (Scheme 2ꢀ1). While
substrate 1a was treated with diaryliodonium salts 2q, product 3b was obtained in 80%
yield and no product 3q was observed (Scheme 2ꢀ2).
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O
4
5
6
7
N
OTf
O
N
I
OH
N
tꢀBuOK
N
N
+
OH
1)
DCE, 80 ꢀ100 °C
N
1a
2p
3p (<5% yield)
8
9
O
N
O
N
N
N
N
N
O
N
OTf
I
10
11
12
13
14
15
16
17
18
19
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OH
2)
N
tꢀBuOK
DCE, 80 ꢀ100 °C
OMe
+
OH
+
OH
N
S
S
MeO
2q
1a
3q (0% yield)
3b (80% yield)
Scheme 2. No desired products for two diaryliodonium salts 2p and 2q.
Subsequently, the scope of 3ꢀhydroxy benzo[1,2,3]triazinꢀ4(3H)ꢀone 1 was tested
to examine its effect on the formation of desired products 3. As shown in Table 3,
various of 3ꢀhydroxy benzo[1,2,3]triazinꢀ4(3H)ꢀones 1 was tolerated different
substituted groups either 6, 7, or 8ꢀposition on the aryl ring, such as methyl, fluorine,
chlorine and iodine (3abꢀ3ah). Product 3 was obtained from moderate to good yields.
However, when the substituted groups were presented in 7ꢀposition of aryl ring, the
yields decreased obviously (3af and 3ag).
Table 3. The scope of 3ꢀhydroxybenzo[1,2,3]triazinꢀ4(3H)ꢀonea,b
O
O
N
4
5
R
3
N
OH
2
tꢀBuOK
N
6
R
7
+
Ph2IOTf
N
DCE, 80 °C
N
OH
N
1
8
1
2a
3
1a
1b
1c
1d
1e
1f
1g
R = H ( ); 6ꢀMe ( ); 6ꢀI ( ); 6ꢀCl ( ); 6ꢀF ( ); 7ꢀF ( ); 7, 8ꢀMe2 ( );
8ꢀMe (1h);
O
N
O
N
O
N
O
N
Cl
I
Me
H
N
N
N
N
N
N
N
N
OH
OH
OH
OH
3a (88%)
3ab (61%)
3ac (79%)
3ad (70%)
O
O
O
O
F
N
N
N
N
N
N
N
N
N
F
N
Me
OH
N
N
Me
OH
Me
OH
OH
3ae
3af
3ag
3ah
(74%)
(62%)
(48%)
(35%)
a Reaction conditions: 1 (0.5 mmol), Ph2IOTf (0.75 mmol, 1.5 equiv), tꢀBuOK (0.75
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mmol, 1.5 equiv), DCE (5 mL), 80 ˚C, 18ꢀ24 h; b Isolated yield.
5
6
7
8
9
The Oꢀarylation intermediate 4a was isolated when the reaction was run at 50 ˚C.
Intermediate 4a could be converted into 3a in 90% yield at 80 ˚C for 2 h, as illustrated
in Scheme 3ꢀ1. To have a better understanding of the [3,3]ꢀrearrangement steps, we
tested two other productꢀbased mechanistic experiments. As shown in Scheme 3ꢀ2, no
crossover products were observed when the mixture of 4c and 4ac was run at 80 ˚C
for 3 h. This result suggests that the [3,3]ꢀrearrangement might be an intramolecular
process. When radical trap TEMPO (2.0 equiv) was added in the optimal condition or
heated with Oꢀarylation intermediate 4a, analogue yield of 3a was obtained (Scheme
3ꢀ3), which demonstrates that the NꢀO bond cleavage might not proceed in radical
process.
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O
1) Preparation of Oꢀarylation product 4a
N
N
O
O
OH
O
tꢀBuOK
N
N
N
N
N
Ph
+
Ph2IOTf
+
OH
DCE, 50 °C
N
N
4a (64%)
1a
3a (20%)
80 °C
90% yield
O
O
2) Crossꢀover experiment
O
N
N
N
N
N
N
OH
O
N
Cl
OH
N
N
Cl
DCE, 80 °C
4c
3e (85%)
3a (0%)
O
+
O
O
I
I
N
N
I
O
N
N
N
N
N
N
N
OH
OH
4ac
Cl
3ac (80%)
3ac' (0%)
O
N
3) Radical trap
O
N
N
OH
tꢀBuOK
N
Me
Me
Me
Ph2IOTf
+
+
N
OH
N
Me
O
DCE, 50 °C
N
1a
3a (85%)
O
O
O
N
N
Ph
DEC, 80 °C
2 h
Me
Me
Me
Me
N
N
O
+
N
N
N
4a
OH
3a (88%)
Scheme 3. Mechanism studies
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Based on the above experimental results, a proposed mechanism for synthesis of
product 3a from substrate 1a with diaryliodonium salt 2a is illustrated in Scheme 4.
Deprotonation of substrate 1a gives intermediate A.20 IntꢀA goes through a
substitution to form iodonium salt B which proceeds a 1,2ꢀphenyl migration to
provide Oꢀarylation product 4a,19,21 then 4a undergoes [3,3]ꢀrearrangement and
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hydrogen migration to give product 3a. 22
O
O
O
OH
OK
O
I
Ph
Ph2IOTf
N
N
N
N
N
N
tꢀBuOK
Ph
N
N
N
1a
A
B
O
O
N
O
Ph
[3,3]ꢀrearrangement
1,2ꢀmigration
N
N
N
N
N
OH
4a
3a
Scheme 4 Proposed mechanism
In order to show the usefulness of this new transformation, gram scale reaction
was performed in the optimal condition (Scheme 5). When 3.2 g (20 mmol) of
substrate 1a reacted with diphenyliodonium salt 2a, product 3a was obtained with
2.87 g in 60% yield, which would allow these compounds to be studied more easily
for their reactivity and further applications.
O
O
N
N
OH
tꢀBuOK
N
N
N
Ph2IOTf
+
OH
DCE, 80 °C
N
2a
1a
(3.2 g, 20 mmol)
3a
(2.87 g, 60% yield)
Scheme 5. Gram scale reaction.
In summary, we have shown that Nꢀaryl benzo[1,2,3]triazinꢀ4(1H)ꢀone derivatives
can be prepared in good yields via a simple and mild oneꢀpot reaction of Oꢀarylation
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of 3ꢀhydroxy benzo[1,2,3]triazinꢀ4(3H)ꢀone with diaryliodonium salts and sequence
of [3,3]ꢀrearrangement. The reaction was tolerated not only a variety of electronꢀrich
or electronꢀdeficient substituents on diaryliodonium salts but also sensitive functional
groups such as halides, nitro, ester, aldehyde. The mechanism studies showed that the
cleavage of N−O bond might be an intramolecular process via [3,3]ꢀrearrangement.
The reaction was easily up to gram scale. The feature of present protocol was that new
C−O and C−N bonds were formed by Oꢀarylation and [3,3]ꢀrearrangement in oneꢀpot
reaction under metalꢀfree, mild and simple conditions.
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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, 500, or 600 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
chromatography was performed on silica gel (300ꢀ400 mesh).
General procedure for preparing Nꢀaryl benzo[1,2,3]triazinꢀ4(1H)ꢀones 3: A
Schlenk tube, open to air, was charged with 1 (0.5 mmol), and DCE (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
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(0.75 mmol, 1.5 equiv) was added in one portion. The reaction was stirred at 80 ˚C or
100 ˚C and monitored by TLC until 1 was consumed completely (18ꢀ24 h). At this
time, the DCE was removed under reduced pressure and the crude product was
purified by flash chromatography (the crude residue was dry loaded with silica gel)
using gradient eluent (ethyl acetate/petroleum ether = 1/10 to 1/1) to provide product
3 as brown solid.
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1ꢀ(2ꢀHydroxyphenyl)benzo[1,2,3]triazinꢀ4(1H)ꢀone (3a), 0.105 g, 88% yield,
brown solid, mp: 148ꢀ149 °C. 1H NMR (400 MHz, CDCl3): δ 12.30 (s, 1H), 8.49 (d, J
= 8.4 Hz, 1H), 8.39 (d, J = 7.6 Hz, 1H), 8.04 (d, J = 8.0 Hz, 1H), 7.98 (t, J = 7.2 Hz,
1H), 7.90 (t, J = 7.2 Hz, 1H), 7.50 (t, J = 7.6 Hz, 1H), 7.19 (d, J = 8.0 Hz, 1H), 7.05 (t,
13
J = 7.6 Hz, 1H); C NMR (100 MHz, CDCl3): δ 165.0, 153.5, 145.1, 135.0, 134.2,
134.0, 129.4, 127.0, 125.7, 123.1, 120.4, 120.0, 118.5; IR (thin film) 3425, 3064,
1673, 1606, 1473, 1259, 754, 671 cm‒1; HRMS (ESI) m/z calcd. for C13H10N3O2
(M+H)+ 240.0773, found 240.0768.
1ꢀ(2ꢀHydroxyꢀ5ꢀmethoxyphenyl)benzo[1,2,3]triazinꢀ4(1H)ꢀone (3b), 0.113 g, 84%
1
yield, brown solid, mp: 120ꢀ121 °C. H NMR (500 MHz, CDCl3): δ 11.94 (s, 1H),
8.40 (d, J = 7.5 Hz, 1H), 8.03 (d, J = 8.0 Hz, 1H), 7.97−7.94 (m, 2H), 7.89 (t, J = 7.5
Hz, 1H), 7.12 (s, 2H), 3.88 (s, 3H); 13C NMR (125 MHz, CDCl3): δ 165.2, 152.9,
148.1, 145.2, 135.0, 133.9, 128.9, 126.8, 125.8, 122.8, 121.3, 118.5, 105.8, 56.1; IR
(thin film) 3559, 3069, 2931, 1662, 1632, 1498, 1261, 771 cm‒1; HRMS (ESI) m/z
calcd. for C14H10N3O3 (M−H)− 268.0722, found 268.0716.
1ꢀ(2ꢀHydroxyꢀ5ꢀmethylphenyl)benzo[1,2,3]triazinꢀ4(1H)ꢀone (3c), 0.108 g, 86%
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yield, brown solid, mp: 144ꢀ145 °C. H NMR (500 MHz, CDCl3): δ 12.04 (s, 1H),
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8
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8.39 (d, J = 8.0 Hz, 1H), 8.27 (s, 1H), 8.03 (d, J = 8.0 Hz, 1H), 7.97−7.94 (m, 1H),
7.89 (t, J = 7.5 Hz, 1H), 7.30 (d, J = 8.5 Hz, 1H), 7.09 (d, J = 8.5 Hz, 1H), 2.39 (s,
3H); 13C NMR (125 MHz, CDCl3): δ 165.2, 151.4, 145.2, 135.3, 134.9, 133.8, 129.7,
129.1, 126.8, 125.8, 122.8, 120.2, 118.5, 20.5; IR (thin film) 3440, 3074, 2919, 1663,
1596, 1500, 1267, 780 cm‒1; HRMS (ESI) m/z calcd. for C14H10N3O2 (M−H)−
252.0773, found 252.0767.
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1ꢀ(5ꢀtertꢀButylꢀ2ꢀhydroxyphenyl)benzo[1,2,3]triazinꢀ4(1H)ꢀone (3d), 0.115 g, 78%
1
yield, brown solid, mp: 164ꢀ165 °C. H NMR (600 MHz, CDCl3): δ 12.06 (s, 1H),
8.44 (d, J = 1.8 Hz, 1H), 8.39 (d, J = 7.8 Hz, 1H), 8.06 (d, J = 7.8 Hz, 1H), 7.97 (t, J =
7.2 Hz, 1H), 7.88 (t, J = 7.2 Hz, 1H), 7.54 (dd, J = 8.4 Hz, 1.8 Hz, 1H), 7.13 (d, J =
8.4 Hz, 1H), 1.38 (s, 9H); 13C NMR (150 MHz, CDCl3): δ 165.3, 151.3, 145.3, 143.4,
135.0, 133.9, 131.9, 128.9, 127.0, 125.8, 120.1, 119.4, 118.5, 34.4, 31.3; IR (thin film)
3442, 3069, 2962, 1670, 1505, 1462, 1266, 774 cm‒1; HRMS (ESI) m/z calcd. for
C17H16N3O2 (M−H)− 294.1243, found 294.1236.
1ꢀ(5ꢀChloroꢀ2ꢀhydroxyphenyl)benzo[1,2,3]triazinꢀ4(1H)ꢀone (3e), 0.116 g, 85%
1
yield, brown solid, mp: 189ꢀ190 °C. H NMR (400 MHz, CDCl3): δ 12.37 (s, 1H),
8.52 (d, J = 2.0 Hz, 1H), 8.41 (d, J = 7.6 Hz, 1H), 8.07 (d, J = 8.0 Hz, 1H), 8.02−7.98
(m, 1H), 7.94−7.90 (m, 1H), 7.46 (dd, J = 8.8 Hz, 2.0 Hz, 1H), 7.17 (d, J = 8.8 Hz,
1H); 13C NMR (100 MHz, CDCl3): δ 164.8, 152.3, 145.0, 135.3, 134.5, 134.2, 129.3,
127.2, 125.9, 124.9, 122.6, 121.9, 118.7; IR (thin film) 3439, 3064, 1644, 1606, 1475,
1243, 773, 679 cm‒1; HRMS (ESI) m/z calcd. for C13H9N3O2Cl (M+H)+ 274.0383,
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1ꢀ(5ꢀFluoroꢀ2ꢀhydroxyphenyl)benzo[1,2,3]triazinꢀ4(1H)ꢀone (3f), 0.109 g, 85%
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yield, brown solid, mp: 173ꢀ174 °C. H NMR (500 MHz, CDCl3): δ 12.17 (s, 1H),
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8.42 (d, J = 8.0 Hz, 1H), 8.26 (dd, J = 9.5 Hz, 2.5 Hz, 1H), 8.05 (d, J = 8.5 Hz, 1H),
8.00−7.97 (m, 1H), 7.93 (t, J = 7.5 Hz, 1H), 7.24−7.23 (m, 1H), 7.19−7.16 (m, 1H);
13C NMR (125 MHz, CDCl3): δ 164.8, 156.4 (d, J = 239.0 Hz), 150.1, 145.1, 135.2,
134.4, 127.1, 125.9, 122.0 (d, J = 24.0 Hz), 121.7, 121.6, 118.7, 109.5 (d, J = 28.0
Hz); IR (thin film) 3429, 3080, 1679, 1598, 1498, 1247, 771, 676 cm‒1; HRMS (ESI)
m/z calcd. for C13H9N3O2F (M+H)+ 258.0679, found 258.0670.
1ꢀ(2ꢀHydroxyꢀ4ꢀnitrophenyl)benzo[1,2,3]triazinꢀ4(1H)ꢀone (3g), 0.083 g, 59%
1
yield, brown solid, mp: 248ꢀ249 °C. H NMR (600 MHz, CDCl3): δ 12.69 (s, 1H),
8.72 (d, J = 9.6 Hz, 1H), 8.44 (d, J = 7.8 Hz, 1H), 8.11 (d, J = 8.4 Hz, 1H), 8.06−8.03
13
(m, 2H), 7.99 (t, J = 7.2 Hz, 1H), 7.88 (dd, J = 9.0 Hz, 1.8 Hz, 1H); C NMR (150
MHz, CDCl3): δ 164.5, 154.1, 150.6, 145.0, 135.6, 135.3, 132.9, 127.5, 126.1, 124.7,
119.0, 116.3, 114.2; IR (thin film) 3430, 3066, 1646, 1573, 1524, 1464, 1248, 775
cm‒1; HRMS (ESI) m/z calcd. for C13H7N4O4 (M−H)− 283.0468, found 283.0467.
1ꢀ(2ꢀHydroxyꢀ3ꢀmethylphenyl)benzo[1,2,3]triazinꢀ4(1H)ꢀone (3h), 0.053 g, 42%
1
yield, brown solid, mp: 159ꢀ160 °C. H NMR (600 MHz, CDCl3): δ 12.54 (s, 1H),
8.38 (d, J = 7.8 Hz, 1H), 8.30 (d, J = 8.4 Hz, 1H), 8.00 (d, J = 8.4 Hz, 1H), 7.95−7.93
(m, 1H), 7.87 (t, J = 7.2 Hz, 1H), 7.34 (d, J = 6.6 Hz, 1H), 6.92−6.90 (m, 1H), 2.35 (s,
3H); 13C NMR (150 MHz, CDCl3): δ 165.1, 152.0, 145.3, 135.0, 134.9, 133.9, 129.7,
129.3, 126.9, 125.8, 120.8, 119.1, 118.5, 16.4; IR (thin film) 3428, 3075, 2923, 1682,
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1599, 1467, 1254, 770 cm‒1; HRMS (ESI) m/z calcd. for C14H10N3O2 (M−H)−
252.0773, found 252.0767.
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1ꢀ(2ꢀHydroxyꢀ5ꢀphenoxyphenyl)benzo[1,2,3]triazinꢀ4(1H)ꢀone (3i), 0.124 g, 75%
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yield, brown solid, mp: 162ꢀ163 °C. H NMR (600 MHz, CDCl3): δ 12.18 (s, 1H),
8.39 (d, J = 7.8 Hz, 1H), 8.20 (d, J = 2.4 Hz, 1H), 7.98 (d, J = 8.4 Hz, 1H), 7.95 (t, J =
7.2 Hz, 1H), 7.89 (t, J = 7.2 Hz, 1H), 7.36 (t, J = 7.8 Hz, 2H), 7.22−7.17 (m, 2H),
13
7.12 (t, J = 7.2 Hz, 1H), 7.01 (d, J = 7.8 Hz, 2H); C NMR (150 MHz, CDCl3): δ
165.0, 157.6, 150.0, 149.3, 145.1, 135.1, 134.2, 129.9, 129.8, 127.2, 126.5, 125.8,
123.3, 121.6, 118.6, 117.8, 113.7; IR (thin film) 3432, 3061, 1734, 1596, 1484, 1210,
771, 680 cm‒1; HRMS (ESI) m/z calcd. for C19H12N3O3 (M−H)− 330.0879, found
330.0871.
1ꢀ(4ꢀHydroxybiphenylꢀ3ꢀyl)benzo[1,2,3]triazinꢀ4(1H)ꢀone (3j), 0.134 g, 85% yield,
brown solid, mp: 194ꢀ195 °C. 1H NMR (600 MHz, CDCl3): δ 12.32 (s, 1H), 8.67 (d, J
= 1.8 Hz, 1H), 8.38 (d, J = 7.8 Hz, 1H), 8.04 (d, J = 7.8 Hz, 1H), 7.97−7.94 (m, 1H),
7.88−7.86 (m, 1H), 7.71 (dd, J = 8.4 Hz, 1.8 Hz, 1H), 7.61 (d, J = 7.8 Hz, 2H), 7.47 (t,
13
J = 7.2 Hz, 2H), 7.37 (t, J = 7.2 Hz, 1H), 7.24 (d, J = 8.4 Hz, 1H); C NMR (150
MHz, CDCl3): δ 165.1, 152.9, 145.2, 139.2, 135.1, 134.1, 133.5, 133.0, 129.5, 128.9,
127.5, 127.1, 126.7, 125.8, 121.3, 121.0, 118.6; IR (thin film) 3434, 3035, 1673, 1600,
1480, 1294, 761 cm‒1; HRMS (ESI) m/z calcd. for C19H12N3O2 (M−H)− 314.0930,
found 314.0916.
1ꢀ(2ꢀHydroxyꢀ5ꢀisopropylphenyl)benzo[1,2,3]triazinꢀ4(1H)ꢀone (3k), 0.109 g, 78%
yield, brown solid, mp: 170ꢀ171 °C. 1H NMR (600 MHz, DMSOꢀd6): δ 10.43 (s, 1H),
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8.23 (d, J = 8.4 Hz, 1H), 8.10−8.05 (m, 2H), 8.00−7.98 (m, 1H), 7.61 (d, J = 1.8 Hz,
1H), 7.36−7.35 (m, 1H), 7.07 (d, J = 8.4 Hz, 1H), 2.93−2.89 (m, 1H), 1.22 (d, J = 7.2
Hz, 6H); 13C NMR (150 MHz, DMSOꢀd6): δ 166.9, 148.8, 146.5, 139.9, 135.5, 135.1,
134.6, 130.3, 127.2, 125.1, 123.2, 118.2, 117.8, 32.9, 24.3; IR (thin film) 3433, 3043,
2956, 2868, 1674, 1571, 1460, 1266, 774 cm‒1; HRMS (ESI) m/z calcd. for
C16H14N3O2 (M−H)− 280.1086, found 280.1080.
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1ꢀ(5ꢀBromoꢀ2ꢀhydroxyphenyl)benzo[1,2,3]triazinꢀ4(1H)ꢀone (3l), 0.108 g, 68%
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yield, brown solid, mp: 201ꢀ202 °C. H NMR (500 MHz, CDCl3): δ 12.37 (s, 1H),
8.66 (d, J = 2.0 Hz, 1H), 8.42 (d, J = 7.5 Hz, 1H), 8.07 (d, J = 8.5 Hz, 1H), 8.01 (t, J =
7.5 Hz, 1H), 7.93−7.90 (m, 1H), 7.58 (dd, J = 8.5 Hz, 2.0 Hz, 1H), 7.11 (d, J = 9.0 Hz,
1H); 13C NMR (125 MHz, CDCl3): δ 164.8, 152.8, 145.1, 137.0, 135.2, 134.5, 129.8,
127.2, 125.9, 125.6, 122.3, 118.8, 111.6; IR (thin film) 3430, 3071, 1681, 1599, 1474,
1294, 772, 678 cm‒1; HRMS (ESI) m/z calcd. for C13H7N3O2Br (M−H)− 315.9722,
found 315.9713.
1ꢀ(4ꢀBromoꢀ2ꢀhydroxyphenyl)benzo[1,2,3]triazinꢀ4(1H)ꢀone (3m), 0.099 g, 63%
1
yield, brown solid, mp: 166ꢀ167 °C. H NMR (500 MHz, CDCl3): δ 12.49 (s, 1H),
8.39−8.35 (m, 2H), 8.03 (d, J = 8.0 Hz, 1H), 7.99−7.96 (m, 1H), 7.91 (t, J = 7.0 Hz,
13
1H), 7.37 (s, 1H), 7.17 (d, J = 9.0 Hz, 1H); C NMR (125 MHz, CDCl3): δ 164.8,
154.1, 145.1, 135.2, 134.3, 128.5, 128.4, 127.0, 125.9, 124.2, 123.5, 123.4, 118.7; IR
(thin film) 3429, 3061, 1647, 1600, 1569, 1465, 1236, 766 cm‒1; HRMS (ESI) m/z
calcd. for C13H7N3O2Br (M−H)− 315.9722, found 315.9713.
Methyl 4ꢀhydroxyꢀ3ꢀ(4ꢀoxobenzo[1,2,3]triazinꢀ1(4H)ꢀyl)benzoate (3n), 0.109 g, 74%
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yield, brown solid, mp: 159ꢀ160 °C. H NMR (600 MHz, CDCl3): δ 12.87 (s, 1H),
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8
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9.17 (d, J = 1.2 Hz, 1H), 8.39 (d, J = 7.8 Hz, 1H), 8.12 (d, J = 7.8 Hz, 2H), 8.01 (t, J =
7.8 Hz, 1H), 7.93 (t, J = 7.8 Hz, 1H), 7.21 (d, J = 8.4 Hz, 1H), 3.96 (s, 3H); 13C NMR
(150 MHz, CDCl3): δ 165.4, 164.6, 157.1, 145.0, 135.2, 134.7, 134.5, 128.8, 127.3,
125.7, 125.4, 122.2, 120.6, 118.7, 52.3; IR (thin film) 3416, 3070, 2966, 1732, 1685,
1613, 1431, 293, 765 cm‒1; HRMS (ESI) m/z calcd. for C15H10N3O4 (M−H)−
296.0671, found 296.0675.
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4ꢀHydroxyꢀ3ꢀ(4ꢀoxobenzo[1,2,3]triazinꢀ1(4H)ꢀyl)benzaldehyde (3o), 0.061 g, 46%
1
yield, brown solid, mp: 183ꢀ184 °C. H NMR (600 MHz, CDCl3): δ 13.12 (s, 1H),
9.99 (s, 1H), 9.05 (d, J = 1.2 Hz, 1H), 8.41 (d, J = 7.8 Hz, 1H), 8.13 (d, J = 8.4 Hz,
2H), 8.04−8.01 (m, 2H), 7.96 (t, J = 7.2 Hz, 1H), 7.33 (d, J = 9.0 Hz, 1H); 13C NMR
(150 MHz, CDCl3): δ 189.3, 164.5, 158.4, 144.9, 135.4, 134.7, 134.0, 129.3, 129.1,
127.3, 126.2, 125.9, 121.5, 118.8; IR (thin film) 3428, 3063, 2808, 2720, 1692, 1642,
1603, 1572, 1252, 771 cm‒1; HRMS (ESI) m/z calcd. for C14H8N3O3 (M−H)−
266.0566, found 266.0556.
1ꢀ(2ꢀHydroxyphenyl)ꢀ6ꢀmethylbenzo[1,2,3]triazinꢀ4(1H)ꢀone (3ab), 0.077 g, 61%
yield, brown solid, mp: 188ꢀ189 °C. 1H NMR (600 MHz, DMSOꢀd6): δ 10.71 (s, 1H),
8.02 (s, 1H), 8.00 (d, J = 8.4 Hz, 1H), 7.90 (d, J = 7.8 Hz, 1H), 7.74 (d, J = 7.8 Hz,
1H), 7.48 (t, J = 7.2 Hz, 1H), 7.14 (d, J = 7.8 Hz, 1H), 7.04 (t, J = 7.2 Hz, 1H), 2.58
13
(s ,3H); C NMR (150 MHz, DMSOꢀd6): δ 166.6, 151.0, 146.0, 144.7, 136.9, 135.3,
132.3, 127.2, 125.8, 124.3, 119.6, 118.3, 117.8, 22.2; IR (thin film) 3427, 3031, 2871,
1665, 1609, 1482, 1293, 1256, 758 cm‒1; HRMS (ESI) m/z calcd. for C14H10N3O2
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(M−H)− 252.0773, found 252.0767.
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1ꢀ(2ꢀHydroxyphenyl)ꢀ6ꢀiodobenzo[1,2,3]triazinꢀ4(1H)ꢀone (3ac), 0.144 g, 79%
yield, brown solid, mp: 203ꢀ204 °C. 1H NMR (500 MHz, DMSOꢀd6): δ 10.66 (s, 1H),
8.50 (d, J = 1.0 Hz, 1H), 8.37 (dd, J = 8.5 Hz, 1.0 Hz, 1H), 7.85 (d, J = 8.5 Hz, 1H),
7.72 (d, J = 7.5 Hz, 1H), 7.48−7.45 (m, 1H), 7.13 (d, J = 8.5 Hz, 1H), 7.02 (t, J = 7.5
Hz, 1H); 13C NMR (125 MHz, DMSOꢀd6): δ 165.4, 150.9, 145.6, 144.1, 135.5, 133.6,
132.5, 128.8, 125.8, 119.6, 118.8, 118.4, 102.4; IR (thin film) 3421, 3066, 1655, 1609,
1583, 1478, 1248, 756 cm‒1; HRMS (ESI) m/z calcd. for C13H7N3O2I (M−H)−
363.9583, found 363.9575.
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6ꢀChloroꢀ1ꢀ(2ꢀhydroxyphenyl)benzo[1,2,3]triazinꢀ4(1H)ꢀone (3ad), 0.095 g, 70%
1
yield, brown solid, mp: 190ꢀ191 °C. H NMR (600 MHz, CDCl3): δ 12.12 (s, 1H),
8.43 (d, J = 8.4 Hz, 1H), 8.32 (d, J = 1.2 Hz, 1H), 7.98 (d, J = 9.0 Hz, 1H), 7.89 (dd, J
= 9.0 Hz, 1.8 Hz, 1H), 7.48 (t, J = 7.2 Hz, 1H), 7.17 (d, J = 7.8 Hz, 1H), 7.03 (t, J =
7.8 Hz, 1H); 13C NMR (150 MHz, CDCl3): δ 163.9, 153.6, 143.6, 140.5, 135.9, 134.4,
129.4, 128.6, 125.3, 123.1, 120.6, 120.2, 119.4; IR (thin film) 3422, 3067, 1648, 1606,
1575, 1480, 1241, 759 cm‒1; HRMS (ESI) m/z calcd. for C13H7N3O2Cl (M−H)−
272.0227, found 272.0221.
6ꢀFluoroꢀ1ꢀ(2ꢀhydroxyphenyl)benzo[1,2,3]triazinꢀ4(1H)ꢀone (3ae), 0.079 g, 62%
1
yield, brown solid, mp: 153ꢀ154 °C. H NMR (600 MHz, CDCl3): δ 12.14 (s, 1H),
8.44 (d, J = 8.4 Hz, 1H), 8.10 (dd, J = 8.4 Hz, 4.8 Hz, 1H), 8.01 (dd, J = 7.8 Hz, 2.4
Hz, 1H), 7.70−7.67 (m, 1H), 7.49 (t, J = 7.2 Hz, 1H), 7.18 (d, J = 8.4 Hz, 1H), 7.04 (t,
J = 7.8 Hz, 1H); 13C NMR (150 MHz, CDCl3): δ 166.2 (d, J = 259.0 Hz), 164.4 (d, J
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= 3.3 Hz), 153.4, 142.0, 134.2, 130.4 (d, J = 8.8 Hz), 129.3, 124.5 (d, J = 25.0 Hz),
123.0, 120.5, 120.1, 111.0, 110.9; IR (thin film) 3428, 3050, 1654, 1612, 1575, 1477,
1246, 762 cm‒1; HRMS (ESI) m/z calcd. for C13H7N3O2F (M−H)− 256.0523, found
256.0517.
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7ꢀFluoroꢀ1ꢀ(2ꢀhydroxyphenyl)benzo[1,2,3]triazinꢀ4(1H)ꢀone (3af), 0.061 g, 48%
1
yield, brown solid, mp: 182ꢀ183 °C. H NMR (600 MHz, CDCl3): δ 12.15 (s, 1H),
8.45 (d, J = 8.4 Hz, 1H), 8.42−8.39 (m, 1H), 7.65ꢀ7.64 (m, 1H), 7.60−7.57 (m, 1H),
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7.50 (t, J = 7.2 Hz, 1H), 7.18 (d, J = 8.4 Hz, 1H). 7.05 (t, J = 7.8 Hz, 1H); C NMR
(150 MHz, CDCl3): δ 167.1 (d, J = 255.0 Hz), 164.3, 153.7, 147.0 (d, J = 13.0 Hz),
134.6, 129.4, 128.9 (d, J = 9.9 Hz), 123.2, 123.1 (d, J = 24.0 Hz), 120.6, 120.2, 115.2,
111.8 (d, J = 22.9 Hz); IR (thin film) 3430, 3063, 1646, 1611, 1584, 1479, 1246, 763
cm‒1; HRMS (ESI) m/z calcd. for C13H9N3O2F (M+H)+ 258.0679, found 258.0675.
1ꢀ(2ꢀHydroxyphenyl)ꢀ7,8ꢀdimethylbenzo[1,2,3]triazinꢀ4(1H)ꢀone (3ag), 0.046 g,
1
35% yield, brown solid, mp: 193ꢀ194 °C. H NMR (600 MHz, CDCl3): δ 12.42 (s,
1H), 8.43 (d, J = 8.4 Hz, 1H), 8.11 (d, J = 8.4 Hz, 1H), 7.64 (d, J = 8.4 Hz, 1H), 7.46
(t, J = 7.2 Hz, 1H), 7.17 (d, J = 8.4 Hz, 1H), 7.03 (t, J = 7.8 Hz, 1H), 2.67 (s, 3H),
2.51 (s, 3H); 13C NMR (150 MHz, CDCl3): δ 165.5, 153.5, 144.4, 143.7, 136.3, 134.7,
133.9, 129.8, 123.0, 122.6, 120.5, 120.0, 116.9, 20.7, 13.2; IR (thin film) 3433, 3035,
2924, 1659, 1602, 1479, 1286, 775 cm‒1; HRMS (ESI) m/z calcd. for C15H12N3O2
(M−H)− 266.0930, found 266.0923.
1ꢀ(2ꢀHydroxyphenyl)ꢀ8ꢀmethylbenzo[1,2,3]triazinꢀ4(1H)ꢀone (3ah), 0.093 g, 74%
1
yield, brown solid, mp: 195ꢀ196°C. H NMR (600 MHz, CDCl3): δ 12.34 (s, 1H),
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8.44 (d, J = 8.4 Hz, 1H), 8.19 (d, J = 7.8 Hz, 1H), 7.75−7.71 (m, 2H), 7.46 (t, J = 7.8
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7
13
Hz, 1H), 7.17 (d, J = 8.4 Hz, 1H), 7.03 (t, J = 7.8 Hz, 1H), 2.76 (s, 3H); C NMR
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(150 MHz, CDCl3): δ 165.4, 153.5, 143.9, 136.9, 135.7, 134.0, 133.8, 129.7, 123.3,
123.1, 120.5, 120.0, 118.8, 17.1; IR (thin film) 3427, 3058, 2923, 1660, 1591, 1478,
1291, 763 cm‒1; HRMS (ESI) m/z calcd. for C14H10N3O2 (M−H)− 252.0773, found
252.0765.
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General procedure for Synthesis of Oꢀarylation product 4: A Schlenk tube was
charged with 1 (0.5 mmol) and DCE (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 was stirred at room temperature for 18ꢀ24 h. At
this time, the DCE was removed under reduced pressure and crude product was
purified by flash chromatography (the crude residue was dry loaded with silica gel)
using gradient eluents (ethyl acetate/petroleum ether 1/10 to 1/6) to provide product 4
as yellow solid.
3ꢀPhenoxybenzo[1,2,3]triazinꢀ4(3H)ꢀone (4a), 0.076 g, 64% yield, yellow solid, mp:
1
114ꢀ115 °C. H NMR (500 MHz, DMSOꢀd6): δ 8.34 (d, J = 8.0 Hz, 2H), 8.18 (t, J =
8.0 Hz, 1H), 8.01 (t, J = 7.5 Hz, 1H), 7.42 (t, J = 8.0 Hz, 2H), 7.21−7.17 (m, 3H); 13C
NMR (125 MHz, DMSOꢀd6): δ 158.9, 151.0, 144.3, 136.3, 133.7, 130.5, 129.2, 125.7,
124.9, 122.9, 114.2; IR (thin film) 3068, 1715, 1585, 1483, 1183, 1160, 751 cm‒1;
HRMS (ESI) m/z calcd. for C13H8O2N3 (M−H)− 238.0617, found 238.0609.
3ꢀ(4ꢀChlorophenoxy)benzo[1,2,3]triazinꢀ4(3H)ꢀone (4c), 0.069 g, 50% yield,
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yellow solid, mp: 120ꢀ121 °C. H NMR (600 MHz, CDCl3): δ 8.41 (d, J = 7.8 Hz,
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1H), 8.27 (d, J = 8.4 Hz, 1H), 8.04 (t, J = 7.8 Hz, 1H), 7.87 (t, J = 7.8 Hz, 1H), 7.33
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9
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(d, J = 9.0 Hz, 2H), 7.13 (d, J = 8.4 Hz, 2H); C NMR (150 MHz, CDCl3): δ 157.3,
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150.7, 144.2, 135.5, 132.8, 130.5, 129.8, 129.1, 125.8, 122.5, 117.1; IR (thin film)
3104, 1722, 1584, 1483, 1187, 1163, 772 cm‒1; HRMS (ESI) m/z calcd. for
C13H7N3O2Cl (M−H)− 272.0227, found 272.0222.
6ꢀIodoꢀ3ꢀphenoxybenzo[1,2,3]triazinꢀ4(3H)ꢀone (4ac), 0.049 g, 27% yield, yellow
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solid, mp: 145ꢀ146 °C. H NMR (600 MHz, CDCl3): δ 8.77 (s, 1H), 8.31 (d, J = 8.4
Hz, 1H), 7.95 (d, J = 8.4 Hz, 1H), 7.37 (t, J = 7.8 Hz, 2H), 7.20 (t, J = 7.8 Hz, 1H),
7.14 (d, J = 7.8 Hz, 2H); 13C NMR (150 MHz, CDCl3): δ 158.7, 149.3, 144.5, 143.3,
134.8, 130.2, 129.9, 125.3, 123.6, 115.3, 99.6; IR (thin film) 3054, 1716, 1586, 1487,
1185, 1163, 751 cm‒1; HRMS (ESI) m/z calcd. for C13H7N3O2I (M−H)− 363.9583,
found 363.9575.
Thermal rearrangement of 4a to 3a: In Schlenk tube was charged with 4a (0.060 g,
0.25 mmol) and DCE (2.5 mL). The mixture was stirred vigorously at 80 ˚C for 3 h.
At this time, the DCE was removed under reduced pressure and the crude product was
purified by flash chromatography (the crude residue was dry loaded with silica gel)
using gradient eluent (ethyl acetate/petroleum ether 1/10 to 1/2) to provide product 3a
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as brown solid (0.054 mg, 90% yield). The H and 13C NMR spectra of 3a were
consistent with the data described above.
Crossꢀover experiment of mixture 4c and 4ac: In Schlenk tube was charged with 4c
(0.027 g, 0.10 mmol) and 4ac (0.036 mg, 0.10 mmol), dissolved in DCE (2.5 mL).
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The mixture was stirred vigorously at 80 ˚C for 3 h. At this time, the DCE was
removed under reduced pressure and the crude product was obtained as brown solid
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(60 mg). H and 13C NMR spectra of the 3e and 3ac in the crude mixture was
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determined by contrast with pure 3e and 3ac which have been characterized above.
The yields were determined by the ratio of 3e (85% yield) and 3ac (80% yield) from
the spectrum. And no crossꢀover products 3a and 3ac’ were observed in the crude
NMR.
Gram scale reaction: In 250 mL oneꢀneck round bottle flask was charged with 1a
(3.2 g, 20 mmol) and DCE (200 mL). tꢀBuOK (30 mmol, 1.5 equiv) was added in
portions at room temperature. The mixture was stirred vigorously at room temperature
for 5 min. Then, diaryliodonium salts 2a (30 mmol, 1.5 equiv) was also added in
portions. The reaction was stirred at 80˚C and monitored by TLC until 1a was
consumed completely (18 h). At this time, the DCE was removed under reduced
pressure and the crude product was purified by flash chromatography (the crude
residue was dry loaded with silica gel) using gradient eluent (ethyl acetate/petroleum
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ether 1/10 to 1:1) to provide product 3a as brown solid (2.87g, 60% yield). The H
and 13C NMR spectra of 3a were consistent with the data described above.
General procedure for synthesis of Nꢀhydroxyl benzo[1,2,3]triazinꢀ4(3H)ꢀones 1:
O
COOH
NH2
COOMe
NH2
MeOH
H2SO4
NH2OH—HCl
H2
NHOH
R
R
R
O
NH2
S3
S1
S2
O
N
OH
NaNO2
HOAc
N
R
N
1
A mixture of orthoꢀamino benzoic acids S1 (20 mmol), absolute methanol (20
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mL), and concentrated H2SO4 (6 mL) was refluxed for 48 h. After cooling, the
mixture was concentrated to about 10 mL and poured into 15 g of ice. The mixture
was basified with concentrated aqueous ammonia to pH 8ꢀ9 with cooling in an ice
bath, and white precipitate was collected by filtration. The filtrate was extracted with
ether (4 × 50 mL) and the combined ether layer was washed with brine and dried with
Na2SO4. Evaporation of the ether afforded a solid which was recrystallized from
hexane to give S2 as white solid and used directly into the next step.
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Hydroxylamine hydrochloride (10 mmol) was added slowly with stirring and
cooling to aqueous NaOH (10 mL, 1.0 M) solution. To the solution was added S1 (10
mmol) in portions followed by MeOH (10 mL), and the mixture was stirred for 48 h.
The solution was concentrated under reduced pressure and acidified with cooling to
pH 5ꢀ6 with 25% of HCl. The white precipitate was filtered, washed with a small
amount of cold water, and dried in vaccuo to give S2 as a white solid which was pure
enough to the next step.
To a suspension of S2 in water (10 mL) was added concentrated HCl (4 mL) with
stirring. While the mixture cooled in an ice bath, a cold solution of NaNO2 (1.38 g, 20
mmol) in water was added dropwise and the temperature was maintained below 0 °C.
The mixture was further stirring in the ice bath for another 30 min, and the solid was
filtered, washed with a small amount of cold water, and dried to give Nꢀhydroxyl
benzo[1,2,3]triazinꢀ4(3H)ꢀone 1 as a light brown solid.
The substrates 1aꢀc have been reported before and their spectra data matched
literature values: 1aꢀc [23]
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3ꢀHydroxyꢀ6ꢀmethylbenzo[1,2,3]triazinꢀ4(3H)ꢀone (1b), 2.86 g, 80% yield, brown
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solid, mp: 215ꢀ216 °C. H NMR (500 MHz, DMSOꢀd6): δ 8.07 (s, 1H), 7.99 (s, 1H),
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7.83 (s, 1H) (NꢀOH resonance was too broad to be observed); C NMR (125 MHz,
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DMSOꢀd6): δ 151.5, 143.9, 142.7, 136.9, 128.5, 124.3, 121.6, 21.8; IR (thin film)
3394, 3069, 2963, 1669, 1644, 1480, 1223, 840, 698 cm‒1; HRMS (ESI) m/z calcd. for
C8H6N3O2 (M−H)− 176.0460, found 176.0461.
3ꢀHydroxyꢀ6ꢀiodobenzo[1,2,3]triazinꢀ4(3H)ꢀone (1c), 4.32 g, 75% yield, brown
1
solid, mp: 194ꢀ195 °C. H NMR (500 MHz, DMSOꢀd6): δ 8.55 (s, 1H), 8.37 (d, J =
4.5 Hz, 1H), 7.96 (d, J = 5.0 Hz, 1H) (NꢀOH resonance was too broad to be observed);
13C NMR (125 MHz, DMSOꢀd6): δ 150.0, 144.0, 143.3, 133.4, 130.1, 123.0, 100.4;
IR (thin film) 3637, 3079, 1679, 1504, 1454, 1269, 837, 691 cm‒1; HRMS (ESI) m/z
calcd. for C7H3IN3O2 (M−H)− 287.9270, found 287.9273.
6ꢀChloroꢀ3ꢀhydroxybenzo[1,2,3]triazinꢀ4(3H)ꢀone (1d), 1.1 g, 56% yield, brown
1
solid, mp: > 300 °C. H NMR (500 MHz, DMSOꢀd6): δ 8.22 (s, 2H), 8.09 (s, 1H)
13
(NꢀOH resonance was too broad to be observed); C NMR (125 MHz, DMSOꢀd6): δ
150.5, 142.9, 137.3, 135.6, 130.8, 124.2, 123.1; IR (thin film) 3409, 3094, 1714, 1637,
1563, 1459, 1189, 841, 609 cm‒1; HRMS (ESI) m/z calcd. for C7H3ClN3O2 (M−H)−
195.9914, found 195.9912.
6ꢀFluoroꢀ3ꢀhydroxybenzo[d][1,2,3]triazinꢀ4(3H)ꢀone (1e), 1.92 g, 53% yield,
brown solid, mp: 196ꢀ197 °C. 1H NMR (500 MHz, DMSOꢀd6): δ 8.33 (s, 1H), 7.98 (s,
2H) (NꢀOH resonance was too broad to be observed); 13C NMR (125 MHz,
DMSOꢀd6): δ 164.6 (d, J = 252.4 Hz), 150.8, 141.6, 132.3 (d, J = 10.0 Hz), 124.3 (d, J
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= 24.5 Hz), 124.0 (d, J = 10.0 Hz), 110.3 (d, J = 24.5 Hz); IR (thin film) 3647, 3091,
1676, 1650, 1579, 1480, 1236, 835, 732 cm‒1; HRMS (ESI) m/z calcd. for C7H3FN3O2
(M−H)− 180.0209, found 180.0208.
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7ꢀFluoroꢀ3ꢀhydroxybenzo[1,2,3]triazinꢀ4(3H)ꢀone (1f), 0.959 g, 53% yield, brown
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solid, m.p: > 300 °C. H NMR (600 MHz, DMSOꢀd6): δ 13.04 (s, 1H), 8.34 (s, 1H),
8.07 (s, 1H), 7.80 (s, 1H); 13C NMR (150 MHz, DMSOꢀd6): δ 166.6 (d, J = 252.0 Hz),
150.9, 146.1 (d, J = 12.0 Hz), 128.7 (d, J = 9.7 Hz), 121.8 (d, J = 22.9 Hz), 118.8,
113.7 (d, J = 22.9 Hz); IR (thin film) 3466, 3085, 1637, 1595, 1486, 1250, 828, 754
cm‒1; HRMS (ESI) m/z calcd. for C7H3FN3O2 (M−H)− 180.0209, found 180.0210.
3ꢀHydroxyꢀ7,8ꢀdimethylbenzo[1,2,3]triazinꢀ4(3H)ꢀone (1g), 1.1 g, 57% yield,
1
brown solid, mp: 205ꢀ206 °C. H NMR (500 MHz, DMSOꢀd6): δ 12.81 (s, 1H), 7.98
13
(s, 1H), 7.02 (s, 1H), 2.67 (s, 3H), 2.46 (s, 3H); C NMR (125 MHz, DMSOꢀd6): δ
151.4, 144.5, 142.4, 135.8, 134.6, 121.9, 119.6, 20.5, 13.1; IR (thin film) 3434, 3077,
2926, 1638, 1561, 1442, 1251, 1080, 702 cm‒1; HRMS (ESI) m/z calcd. for C9H8N3O2
(M−H)−190.0617, found 190.0608.
3ꢀHydroxyꢀ8ꢀmethylbenzo[1,2,3]triazinꢀ4(3H)ꢀone (1h), 0.461 g, 26% yield, brown
solid, mp: 250ꢀ251 °C. 1H NMR (500 MHz, DMSOꢀd6): δ 12.89 (s, 1H), 8.06 (s, 1H),
7.86 (s, 1H), 7.64 (s, 1H), 3.38 (s, 3H); 13C NMR (125 MHz, DMSOꢀd6): δ 151.4,
142.5, 137.7, 136.0, 132.6, 122.8, 121.7, 17.2; IR (thin film) 3416, 3079, 2996, 1666,
1641, 1468, 1239, 766 cm‒1; HRMS (ESI) m/z calcd. for C8H6N3O2 (M−H)− 176.0460,
found 176.0451.
General procedure for synthesis of diaryliodonium salts 2
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Aryl boronic acid (10 mmol, 1.0 equiv) and CH2Cl2 (40 mL) were combined in a
dried roundꢀbottom flask. The mixture was cooled to 0 °C for 5 min, BF3•OEt2 (1.12
mL, 1.10 equiv) was added, and the mixture was stirred for 10 min. A solution of
2ꢀ(diacetoxyiodo)arene (1.05 equiv) in CH2Cl2 (20 mL) was added slowly for 10ꢀ15
min and stirred for additional 10 min. The mixture was warmed to room temperature
and stirred for 1 h. The reaction was cooled to 0 °C again and TfOH (1.67 mL, 1.1
equiv) was dropped into the mixture. Then, the mixture was stirred for 10 min at 0 °C
and warmed to room temperature for additional 10 min. At this time, the solvent was
removed under reduced pressure and the residual ran through a short silica gel column
(about 5 cm) with 5% of MeOH in CH2Cl2 quickly. The mixture was concentrated
under vacuum and Et2O (100 mL) was added to the residual to form a white solid.
Filtrated and obtained the diaryliodonium salts 2 as white solid.
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Some diaryliodonium salts are reported before and their spectra data matched
literature values: 2a, c, o[24], 2b, 2dꢀf and 2h[25], 2g[26], 2j[27], 2l[28], 2m and 2o[29]
,
2p[30]
.
(4ꢀMethoxyphenyl)(4ꢀphenoxyphenyl)iodonium triflate (2i), 3.2 g, 58% yield,
1
white solid, mp: 120ꢀ121 °C. H NMR (500 MHz, DMSOꢀd6): δ 8.18 (d, J = 8.5 Hz,
2H), 8.16 (d, J = 8.5 Hz, 2H), 7.46 (t, J = 8.0 Hz, 2H), 7.26 (t, J = 7.5 Hz, 1H),
7.09−7.04 (m, 6H), 3.80 (s, 3H); 13C NMR (125 MHz, DMSOꢀd6): δ 162.4, 160.6,
155.1, 137.6, 137.5, 130.9, 125.5, 122.4 (q, J = 319.7 Hz), 120.8, 120.5, 117.9, 108.9,
106.2, 56.1; IR (thin film) 3083,2945, 2842, 1575, 1485, 1251, 1168, 829, 638 cm‒1;
HRMS (ESI) m/z calcd. for C19H16IO2 (M−OTf)+ 403.0195, found 403.0194.
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(4ꢀIsopropylphenyl)(4ꢀmethoxyphenyl)iodonium triflate (2k), 2.1 g, 42% yield,
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white solid, mp: 164ꢀ165 °C. H NMR (500 MHz, DMSOꢀd6): δ 8.17 (d, J = 9.0 Hz,
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2H), 8.11 (d, J = 8.5 Hz, 2H), 7.39 (d, J = 8.0 Hz, 2H), 7.07 (d, J = 9.0 Hz, 2H), 3.79
(s, 3H), 2.92−2.90 (m, 1H), 1.16 (d, J = 7.0 Hz, 6H); 13C NMR (125 MHz, DMSOꢀd6):
δ 162.4, 153.3, 137.6, 135.3, 130.2, 122.4 (q, J = 315.1 Hz), 117.9, 114.0, 105.8, 56.1,
33.7, 23.9; IR (thin film) 3086, 2966, 2847, 1577, 1486, 1250, 1167, 830, 639 cm‒1;
HRMS (ESI) m/z calcd. for C16H18OI (M−OTf)+ 353.0402, found 353.0387.
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(4ꢀMethoxyphenyl)(thiophenꢀ3ꢀyl)iodonium triflate (2q), 2.7 g, 59% yield, white
1
solid, mp: 125ꢀ126 °C. H NMR (500 MHz, DMSOꢀd6): δ 8.57 (d, J = 6.5 Hz, 1H),
8.15 (d, J = 9.0 Hz, 2H), 7.79−7.77 (m, 1H), 7.67 (d, J = 4.5 Hz, 1H), 7.08 (d, J = 8.5
Hz, 2H), 3.79 (s, 3H); 13C NMR (125 MHz, DMSOꢀd6): δ 161.8, 136.9, 135.3, 131.4,
130.6, 121.9 (q, J = 320.6 Hz), 117.3, 106.2, 101.5, 55.6; IR (thin film) 3452, 3097,
2970, 2841, 1578, 1488, 1256, 823 cm‒1; HRMS (ESI) m/z calcd. for C11H10IOS
(M−OTf)+ 316.9497, found 316.9486.
ASSOCIATED CONTENT
Supporting Information
Spectra of compounds 3aꢀ3o, 3abꢀ3ah, 4a, 4c, 4ac, 1dꢀh, 2i, 2k, and 2q, this material
is available free of charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Authors
Email for D.ꢀL. M: moeastlight@mailbox.gxnu.edu.cn
Email for G.ꢀF. S: gfysglgx@163.com
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Notes
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The authors declare no competing financial interest.
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ACKNOWLEDGMENT
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Financial support from Oversea 100 Talents Program of Guangxi Education, Basic
Research Program of Guangxi Normal University (grant No. 2014ZD005) and
National Natural Science Foundation of China (21462008), Ministry of Education of
China (IRT1225) and State Key Laboratory Cultivation Base for the Chemistry and
Molecular Engineering of Medicinal Resources, Ministry of Science and Technology
of China (CMEMR2014ꢀA01) are greatly appreciated.
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