One-pot synthesis of polyfunctional pyrazoles: An easy access to α-diazoketones from arylglyoxal monohydrates and tosylhydrazine

Article abstract of DOI:10.1016/j.tet.2014.10.044

A new and efficient method for the generation of α-diazoketones has been developed from arylglyoxal monohydrates and tosylhydrazine at room temperature. 1,3-Dipolar cycloaddition reactions were used to constructing polyfunctional pyrazole derivatives by the reaction of generated α-diazoketones in situ with electron-deficient alkenes, quinones and coumarins in one pot. The one-dimensional molecular packing of 1H-benzo[f]indazole-4,9-dione derivatives along the c direction demonstrated a helical chain formation via N-H?O hydrogen-bonding.

Full text of DOI:10.1016/j.tet.2014.10.044

Tetrahedron 70 (2014) 9321e9329
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One-pot synthesis of polyfunctional pyrazoles: an easy access to
a-diazoketones from arylglyoxal monohydrates and tosylhydrazine
a
a
a
a
a
a
Wen-Ming Shu , Jun-Rui Ma , Kai-Lu Zheng , Hui-Ying Sun , Mei Wang , Yan Yang ,
An-Xin Wu
a
a,b,
*
Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University,
Wuhan 430079, PR China
State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, PR China
b
a r t i c l e i n f o
a b s t r a c t
Article history:
A new and efficient method for the generation of a-diazoketones has been developed from arylglyoxal
Received 2 September 2014
Received in revised form 10 October 2014
Accepted 20 October 2014
Available online 23 October 2014
monohydrates and tosylhydrazine at room temperature. 1,3-Dipolar cycloaddition reactions were used to
constructing polyfunctional pyrazole derivatives by the reaction of generated -diazoketones in situ with
electron-deficient alkenes, quinones and coumarins in one pot. The one-dimensional molecular packing
of 1H-benzo[f]indazole-4,9-dione derivatives along the c direction demonstrated a helical chain for-
mation via NeH/O hydrogen-bonding.
a
Keywords:
Ó 2014 Elsevier Ltd. All rights reserved.
a
-diazoketones
Arylglyoxal monohydrates
Tosylhydrazine
One-pot
Pyrazoles
1
. Introduction
diazoketones was developed by Danheiser and co-workers using
a two-step reaction including the activation of ketones and diazo
4
c,d
In the last few decades,
a
-diazocarbonyl compounds as key in-
transfer procedures (Scheme 1, c).
More recently, Fukuyama and
1
termediates have been extensively applied in organic synthesis.
They are advantageous in their ability to convert to carbenes or
metal carbenoids, which could undertake a variety of useful chem-
ical transformations, including cyclopropanation, XeH (X¼C, O, S, N,
co-workers described an efficient method for the preparation of a-
diazocarbonyl compounds from
a
-bromoacetates or
a
-bromoke-
0
tones with the application of N,N -ditosylhydrazine and DBU
4
e,f
(Scheme 1, d). In this work, a new and simple approach has been
developed for the preparation of -diazoketones from arylglyoxal
1
c,2
etc.) bond insertion, 1,2-shift and ylide formation.
Due to the
-diazocarbonyl compounds have
also beenwidely utilized as 1,3-dipoles in cycloaddition reactions for
a
ability to conserve diazo moiety,
a
monohydrates and tosylhydrazine at room temperature with high
yields (Scheme 1, e).
2
e,2g,3
the construction of nitrogen-containing heterocycles.
Because of their unique and powerful reactivity, various
methods have been proposed for the preparation of -diazo-
ArndteEistert synthesis is generally
accepted as the most common route to acyclic terminal -diazo-
However, diazomethane
and trimethylsilyldiazomethane are toxic and potentially explosive
reagents. The relatively safe alternative routes to -diazocarbonyl
compounds have thus received widespread interest. Wilde and co-
2
. Results and discussion
a
1
a,2,4,5
carbonyl compounds.
Our initial investigation focused on phenylglyoxal monohydrate
a
1a and tosylhydrazine 2. Various base, solvent and temperature were
4
a,5b,6
carbonyl compounds (Scheme 1, a).
screened for the reaction and the subsequent results are summarized
in Table 1. To our delight, -diazophenylketone 3a was obtained in
5% yield when the reaction was performed in CHCl at room tem-
perature for 5 min in the presence of Cs CO (entry 4). However, this
a
a
9
3
2
3
workers reported a two-step process for the preparation of
diazocarbonyl compounds from
Scheme 1, b).4b An improved method for the synthesis of
a
-
reaction provided a very low yield in the absence of base (entry 1). A
variety of bases were screened for the reaction and most bases, in-
cluding K
a
-bromoketones and hydrazine
(
a
-
2 3 2 3 3
CO , Na CO , NaHCO , KOH, NaOH, DABCO, DBU, DMAP
and NEt , were shown to promote the transformation (entries 2, 3,
3
and 5e11). Slightly decreased yields were obtained when the re-
actionwasperformedat highertemperatures (entries12 and13). The
*
Corresponding author. Tel./fax: þ86 (0)27 6786 7773; e-mail address: chwuax@
mail.ccnu.edu.cn (A.-X. Wu).
http://dx.doi.org/10.1016/j.tet.2014.10.044
0
040-4020/Ó 2014 Elsevier Ltd. All rights reserved.

9322
W.-M. Shu et al. / Tetrahedron 70 (2014) 9321e9329
Table 2
Synthesis of a
-diazoketonesa
Scheme 1. Protocols for the synthesis of a-diazocarbonyl compounds.
Table 1
Optimization of the reaction conditions
a
a
Reaction conditions: 1 (1.0 mmol, 1.0 equiv), 2 (1.0 mmol, 1.0 equiv), base
3.0 mmol, 3.0 equiv) in CHCl (2.0 mL) at room temperature for 5 min. The
(
3
ꢀ
Yieldb (%)
yields of the isolated products are shown.
Entry
Solvent
Base
Temp ( C)
1
2
3
4
5
6
7
8
9
CHCl
CHCl
CHCl
3
3
3
d
rt
rt
rt
rt
rt
rt
rt
rt
rt
rt
rt
40
60
rt
rt
rt
rt
rt
rt
rt
rt
15
40
55
95
64
85
81
84
83
89
81
92
94
80
91
55
78
90
65
68
88
K
2
CO
3
Na
Cs
NaHCO
KOH
NaOH
DABCO
DBU
CO
2 3
Excellent yields were achieved with substrates bearing electron-
neutral (H), electron-rich (4-Me, 3-OMe, 4-OMe, 3,4-2OMe, 3,4-
OCH O) and electron-deficient (3-NO , 4-NO ) substituents at-
2 2 2
tached to the benzene ring (90e96%, 3aef, 3l, and 3m). The
transformation also showed a satisfactory level of tolerance to-
wards halogen groups (3gek, 91e96%). In addition, Sterically hin-
CHCl
3
2
CO
3
CHCl
CHCl
CHCl
CHCl
CHCl
CHCl
CHCl
CHCl
CHCl
DMSO
EtOH
2
H O
EtOAc
THF
DMF
3
3
3
3
3
3
3
3
3
3
10
11
12
13
14
15
16
17
18
19
20
21
DMAP
NEt
dered
a-naphthyl, b-naphthyl, and heteroaryl (2-thienyl, 2-
3
benzofuryl) substituted substrates demonstrated good suitability
for the reaction, affording the corresponding products in excellent
yields (3neq, 89e96%). Much to our satisfaction, styryl substituent
groups provided the desired products in 91% yield (3r). The struc-
ture of 3l was further determined by X-ray crystallographic analysis
(see Supplementary data (SD)).
Cs
Cs
Cs
Cs
Cs
Cs
Cs
Cs
Cs
Cs
2
CO
2
CO
2
CO
2
CO
2
CO
2
CO
2
CO
2
CO
2
CO
2
CO
3
3
3
3
3
3
3
3
3
3
Due to the hazardous, potentially explosive, and unstable
Toluene
CH CN
3
6,7
properties of diazocarbonyl compounds, this work aimed to de-
vise a safer and more efficient method for the application of diaz-
ocarbonyl compounds in laboratory and industry settings. Previous
constructions of reactive intermediates in situ have provided wide
Bold emphasizes the optimized reaction conditions.
a
Reaction conditions: 1a (0.1 mmol, 1.0 equiv), 2 (0.1 mmol, 1.0 equiv), base
(
0.3 mmol, 3.0 equiv) and solvent (1 mL). The reaction was performed for 5 min.
7
c,8
b
applications in several important transformations.
Therefore,
Isolated yields.
the generation of diazocarbonyl compounds in situ would be highly
valuable in the synthesis of nitrogenous heterocycles. Similarly,
pyrazole is one of important heterocyclic compound that can be
found in a wide range of natural products and biologically active
screeningof various solvents identified CHCl
while other solvents (DMSO, EtOH, H O, EtOAc, THF, DMF, Toluene
and CH CN) were found to provide lower yields (entries 14e21).
3
as the optimum choice,
2
3
9
With the initial optimized results in hand, the scope of aryl-
molecules. Herein, 1,3-dipolar cycloaddition reactions were used
glyoxal monohydrates (1) was subsequently examined (Table 2).
to construct polyfunctional pyrazole derivatives by the reaction of

W.-M. Shu et al. / Tetrahedron 70 (2014) 9321e9329
9323
in situ generated
quinones and coumarins.
a
-diazoketones with electron-deficient alkenes,
Table 4
Synthesis of 1H-benzo[f]indazole-4,9-dione derivatives in one-pota
With the optimized conditions in hand (Table S1, see Supple-
mentary data (SD)), the scope of the arylglyoxal monohydrates (1)
and electron-deficient alkenes (4) were investigated (Table 3). The
electronic properties of the substituents on the aromatic ring system
were shown to have little influence on the efficiency of this trans-
formation. The arylglyoxal monohydrates bearing electron-neutral
(
2
H), election-rich (4-Me, 4-OMe), electron-deficient (4-NO ), and
halogen(4-Cl,4-Br) groupsunderwentthe processsmoothlytoafford
the desired products 5 in moderate to good yields (86e91%; 5aaefa).
Furthermore, the desired products were also obtained by substrates
with 2-thienyl, sterically hindered
a-naphthyl and b-naphthyl in
moderate to good yields (53e89%; 5gaeia). To our delight, the
electron-deficient alkenes (4) holding cyano and acetyl groups also
successfully performed the reaction (67e77%; 5ac and 5ad). How-
ever, the corresponding product (5ab) could not be obtained with
amide as the electron-withdrawing group. The structure of 5fa was
further determined by X-ray crystallographic analysis (see SI).
Table 3
a
Synthesis of polyfunctional pyrazoles from electron-deficient alkenes in one-pot
naphthyl group, the corresponding desired product (7ja) was
afforded in 92% yield. In addition, the substrate quinones of 6,7-
dimethylnaphthoquinone and 1,4-anthracenedione obtained
yields of 90% and 93%, respectively (7ab and 7ac).
The structure of 7aa was further determined by X-ray crystal-
lographic analysis (Fig. 1, a). To our surprise, the one-dimensional
molecular packing of 7aa along the c direction demonstrated
a right-handed helical chain formation via NeH/O hydrogen-
bonding (Fig. 1, b).
a
Reactions were performed with 1 (1.0 mmol, 1.0 equiv), 2 (1.0 mmol, 1.0
2 3
equiv), 4 (1.5 mmol, 1.5 equiv), and Cs CO (3.0 equiv) in DMSO (20.0 mL)
at 100 °C for 5 hours. The yields of the isolated products are shown.
Encouraged by the results achieved above, it was hoped that the
substrates of this efficient reaction system could also be applied to
quinones (6) (Table 4). Neither the electronic nor steric properties
showed any significant influence on the results of this trans-
formation. The arylglyoxal monohydrates (1) bearing electron-
neutral (H), electron-donating (4-Me, 3-OMe), and electron-
withdrawing (3-NO
vided their corresponding products in excellent yields (80e95%;
aaeca, and 7ha). Good to excellent yields were also obtained for
halo-substituted (2-Cl, 2, 4-2Cl, 3-Br, 4-Br) arylglyoxal substrates
85e95%, 7daega). Furthermore, the substrate with heteroaryl
group 2-thienyl successfully obtained the product in moderate
yield (74%, 7ia). To our satisfaction, when the substrate contained
2
) groups attached to the benzene ring pro-
7
(
Fig. 1. X-ray structural details of 7aa: (a) ORTEP drawing of 7aa; (b) one-dimensional
packing of 7aa along the c direction.
b-

9324
W.-M. Shu et al. / Tetrahedron 70 (2014) 9321e9329
This method was subsequently applied to the construction of
chromeno[3,4-c]pyrazol-4(3H)-one derivatives. The results are
shown in Table 5. As shown, the reaction tolerated a variety of
functional groups and the corresponding product 9 was produced
in good to excellent yields (76e91%; 9aaega). Moreover, coumarin
bearing an electron-donating (6-Me) group afforded the corre-
sponding product in good yield (87%; 9ab). Finally, the structure of
9
aa was confirmed by X-ray crystallographic analysis (see SI).
Table 5
a
Synthesis of chromeno[3,4-c]pyrazol-4(3H)-one derivatives in one-pot
Scheme 3. The possible mechanism of the present reaction.
2 3
the presence of Cs CO . The a-diazophenylethanone 3a could
0
2c
0
transform to the resonance structure 3a . The 3a then reacted
with ethyl acrylate 4a via a 1,3-dipolar cycloaddition reaction
providing the intermediate I. The intermediate I was then oxidized
to afford the intermediate II. Finally, the intermediate II was con-
verted into the desired product 5aa via tautomerization.
3. Conclusion
In summary, a very simple and efficient method has been pro-
posed for the construction of a-diazoketones in high yields under
mild conditions. The 1,3-dipolar cycloaddition reactions were de-
scribed for the construction of polyfunctional pyrazole derivatives
by the reaction of electron-deficient alkenes, quinones and cou-
marins with
a-diazoketones generated in situ from arylglyoxal
monohydrates and tosylhydrazine. Moreover, the one-dimensional
molecular packing of 1H-benzo[f]indazole-4,9-dione derivatives
along the c direction demonstrated a helical chain formation, which
was achieved via NeH/O hydrogen-bonding. Further in-
vestigations into the mechanism and applications of this reaction
are currently underway in our laboratory.
a
Reactions were carried out with 1 (1.2 mmol, 1.2 equiv), 2 (1.2 mmol, 1.2
CO (3.0 equiv) in DMSO (20.0 mL)
equiv), 8 (1.0 mmol, 1.0 equiv), and Cs
at 100 °C for 36 hours. The yields of the isolated products are shown.
2
3
4
4
. Experimental
.1. General
Control experiments were performed to gain an insight into the
reaction process (Scheme 2). The tosylhydrazone compound 10a
allowed a reaction with ethyl acrylate 4a in DMSO at 100 C for 5 h,
and the desired product 5aawas subsequently provided in 87% yield.
The reaction of 3a with 4a was then examined under the same re-
action conditions, affording the desired compound 5aa in 89% yield.
All of the substrates and reagents were commercially available
ꢀ
and used without further purification. TLC analysis was performed
using pre-coated glass plates. Flash column chromatography was
performed on silica gel (200e300 mesh). IR spectra were recorded
ꢁ
1 1
as KBr pellets with absorption in cm . H NMR spectra were de-
ꢀ
termined at 25 C on a Varian Mercury 400 or 600 MHz spec-
trometer. Chemical shifts were provided in parts per million
13
relative to the internal standard of tetramethylsilane (TMS).
spectra were recorded in CDCl or DMSO-d on 100/150 MHz NMR
spectrometers and resonances ( ) in ppm. HRMS were obtained on
C
3
6
d
an Apex-Ultra MS equipped with an atmospheric-pressure chem-
ical ionization source. The melting points were determined using
XT-4 apparatus and recorded without correction. The X-ray crystal-
structures were obtained on a Bruker APEX DUO CCD system.
4.2. General procedure for synthesis of 3 (3a as an example)
A reaction mixture of phenylglyoxal monohydrate 1a (152.2 mg,
Scheme 2. Controlled experiment to prove the mechanism.
1.0 mmol), tosylhydrazine 2 (186.2 mg, 1.0 mmol), and Cs
2 3
CO
(
977.4 mg, 3.0 mmol) in CHCl (2 mL) was stirred at room tem-
3
On the basis of the aforementioned results and reported liter-
perature for 5 min. Water (50 mL) was then added to the mixture.
The organic layer was separated and the aqueous layer was
extracted with EtOAc (50 mLꢂ3). The product was dried over an-
10
ature, a possible mechanism was proposed for the multicompo-
nent reaction, as outlined in Scheme 3 (5aa as example). Initially,
the condensation of phenylglyoxal monohydrate 1a and tosylhy-
drazine 2 afforded the corresponding tosylhydrazone intermediate
2 4
hydrous Na SO and concentrated under reduced pressure. The
residue was purified by column chromatography on silica gel (pe-
troleum ether/EtOAc¼5/1) to afford the desired product 3a.
1
0a, which subsequently generated a-diazophenylethanone 3a in

W.-M. Shu et al. / Tetrahedron 70 (2014) 9321e9329
9325
ꢁ
4
.3. General procedure for synthesis of 5, 9 (5aa as an
1020, 923, 887, 812, 759, 718, 637, 578, 527 cm 1; 1H NMR (600 MHz,
CDCl ):
H), 3.94 (s, 6H); C NMR (100 MHz, CDCl
example)
3
d
(ppm) 7.44 (s,1H), 7.28 (s,1H), 6.87 (d, J¼8.4 Hz,1H), 5.89 (s,
13
1
3
)
d
(ppm) 185.0, 152.7,
þ
A
mixture of phenylglyoxal monohydrate 1a (152.2 mg,
148.9, 129.6, 120.2, 110.0, 109.3, 55.9, 53.5; HRMS (ESI): m/z [MþH]
1.0 mmol), tosylhydrazine 2 (186.2 mg, 1.0 mmol), ethyl acrylate 4a
calcd for C10 : 207.07680; found: 207.07642.
11 2 3
H N O
(
150.1 mg, 1.5 mmol), and Cs
2
CO
3
(977.4 mg, 3.0 mmol) was added
ꢀ
to dried DMSO (20 mL), and stirred at 100 C. After the completion
of the reaction, 100 mL of water was then added to the mixture,
which was then extracted with EtOAc three times (3ꢂ100 mL). The
4.5.6. 1-(Benzo[d][1,3]dioxol-5-yl)-2-diazoethanone
solid; 176.8 mg (yield 93%); mp 96e97 C; IR (KBr): 3451, 3073,
(3f). Yellow
ꢀ
2015, 2381, 2289, 2104, 1621, 1589, 1504, 1448, 1381, 1257, 1109,
ꢁ
1 1
product was dried over anhydrous Na
2
SO
4
and concentrated under
1039, 931, 871, 830, 738, 708, 560, 514 cm
CDCl ):
2H), 5.85 (s, 1H); C NMR (100 MHz, CDCl
; H NMR (600 MHz,
reduced pressure. The residue was then purified by column chro-
matography on silica gel (petroleum ether/EtOAc) to afford the
desired product 5aa.
3
d
(ppm) 7.31e7.26 (m, 2H), 6.82 (d, J¼9.0 Hz, 1H), 6.03 (s,
13
3
)
d
(ppm) 184.7, 151.4,
þ
148.1, 131.1, 122.0, 107.9, 106.9, 101.8, 53.8; HRMS (ESI): m/z [MþH]
calcd for C : 191.04546; found: 191.04512.
9 7 2 3
H N O
4
.4. General procedure for synthesis of 7 (7aa as an example)
4
.5.7. 1-(2-Chlorophenyl)-2-diazoethanone
(3g). Yellow
solid;
ꢀ
A
mixture of phenylglyoxal monohydrate 1a (152.1 mg,
.0 mmol), tosylhydrazine 2 (186.2 mg, 1.0 mmol), naphthoquinone
a (158.2 mg, 1.0 mmol), and Cs CO (977.4 mg, 3.0 mmol) was
added to dried DMSO (20 mL). The resulting mixture was then
stirred at room temperature for 2 h. After the completion of the
reaction,100 mL of water was then added to the mixture, which was
169.8 mg (yield 94%); mp 113e114 C; IR (KBr): 3447, 3073, 2911,
1
6
2104, 1622, 1590, 1504, 1448, 1382, 1257, 1108, 1040, 931, 871, 831,
ꢁ
1 1
2
3
3
738, 708, 559, 514 cm ; H NMR (600 MHz, CDCl ): d (ppm) 7.70 (d,
13
J¼8.6 Hz, 2H), 7.42 (d, J¼8.6 Hz, 2H), 5.89 (s,1H); C NMR (100 MHz,
CDCl
[MþH] calcd for C
3
)
d
(ppm) 184.9,138.9,134.8,128.8,128.0, 54.4;HRMS (ESI): m/z
þ
8 6 2
H ClN O: 181.01651; found: 181.01632.
then extracted with CH
was dried over anhydrous Na
pressure. The residue was purified by column chromatography on
silica gel (petroleum ether/CH Cl ) to afford the desired product 7aa.
Cl
2 2
three times (3ꢂ100 mL). The product
SO and concentrated under reduced
4
4.5.8. 1-(4-Chlorophenyl)-2-diazoethanone (3h).4b Yellow solid;
2
ꢀ
171.6mg(yield95%);mp113e114 C;IR(KBr):3451, 3117, 2925, 2383,
2
2
2288, 2175, 2112, 1610, 1488, 1407, 1379, 1227, 1090, 1011, 870, 835,
ꢁ
1 1
7
56, 670, 521, 469 cm ; H NMR (600 MHz, CDCl ): d (ppm) 7.70 (d,
3
1
3
4
.5. Characterization data
J¼8.6 Hz, 2H), 7.42 (d, J¼8.6 Hz, 2H), 5.89 (s,1H); C NMR (100 MHz,
CDCl
[MþH] calcd for C
3
)
d
þ
(ppm) 184.9,138.9,134.9,128.9,128.1, 54.4; HRMS (ESI): m/z
ClN O: 181.01653; found: 181.01632.
4
.5.1. 2-Diazo-1-phenylethanone (3a).4 Yellow solid; 138.7 mg
8
H
6
2
ꢀ
(
yield 95%); mp 40e41 C; IR (KBr): 3455, 3065, 2109, 1610, 1570,
ꢁ1
1
1448, 1369, 1232, 868, 698, 558, 525 cm
;
H NMR (600 MHz,
4.5.9. 2-Diazo-1-(2,4-dichlorophenyl)ethanone (3i). Yellow solid;
ꢀ
CDCl
3
):
d
(ppm) 7.76 (d, J¼7.8 Hz, 2H), 7.55 (t, J¼7.4 Hz, 1H), 7.45 (t,
195.7 mg (yield 91%); mp 81e82 C; IR (KBr): 3448, 2377, 2111,1624,
13
ꢁ1 1
J¼7.8 Hz, 2H), 5.92 (s,1H); C NMR (100 MHz, CDCl
3
)
d
(ppm) 186.3,
1471, 1354, 1211, 1146, 1104, 1013, 871, 794, 748, 677, 527 cm ; H
NMR (600 MHz, CDCl ):
(ppm) 7.52 (d, J¼7.8 Hz, 1H), 7.43 (s, 1H),
7.32 (d, J¼8.4 Hz,1H), 5.85 (s,1H); C NMR (100 MHz, CDCl
þ
1
C
36.6, 132.7, 128.6, 126.6, 54.2; HRMS (ESI): m/z [MþH] calcd for
3
d
1
3
H
8 7
N
2
O: 147.05550; found: 147.05529.
3
) d (ppm)
1
85.3, 137.4, 135.5, 132.0, 130.4, 130.3, 127.4, 58.1; HRMS (ESI): m/z
.5.2. 2-Diazo-1-(p-tolyl)ethanone (3b).4b Yellow solid; 153.8 mg
[MþH] calcd for C
þ
4
8 5 2 2
H Cl N O: 214.97775; found: 214.97734.
ꢀ
(
yield 96%); mp 49e50 C; IR (KBr): 3450, 3081, 2106, 1604, 1562,
1
5
408, 1373, 1311, 1237, 1188, 1147, 1111, 1016, 871, 829, 735, 677, 574,
4.5.10. 1-(3-Bromophenyl)-2-diazoethanone
213.8 mg (yield 95%); mp 72e73 C; IR (KBr): 3448, 3076, 2385, 2287,
(3j). Yellow solid;
ꢁ1
1
ꢀ
30, 468 cm
;
H NMR (600 MHz, CDCl
3
):
d
(ppm) 7.66 (d,
13
ꢁ1 1
J¼8.2 Hz, 2H), 7.24 (d, J¼8.0 Hz, 2H), 5.89 (s, 1H), 2.40 (s, 3H);
C
2113, 1620, 1562, 1426, 1364, 1223, 888, 798, 721, 523 cm ; H NMR
(600MHz,CDCl ):
(m, 1H), 5.94 (s,1H); C NMR (100 MHz, CDCl
NMR (100 MHz, CDCl
3
)
d
(ppm) 186.00, 143.4, 134.0, 129.2, 126.6,
3
d
(ppm)7.90(s,1H), 7.65(t, J¼7.4Hz, 2H), 7.33e7.29
13
þ
5
3.7, 21.5; HRMS (ESI): m/z [MþH] calcd for C
9
9
H N
2
O: 161.07121;
3
)
d
(ppm) 184.6,138.2,
þ
found: 161.07094.
135.4, 130.1, 129.7, 125.1, 122.8, 54.6; HRMS (ESI): m/z [MþH] calcd
8 6 2
for C H BrN O: 224.96618; found: 224.96580.
4
.5.3. 2-Diazo-1-(3-methoxyphenyl)ethanone
(3c). Yellow
oil;
163.9 mg (yield 93%); IR (KBr): 3452, 3085, 2937, 1604, 1562, 1408,
4.5.11. 1-(4-Bromophenyl)-2-diazoethanone (3k).4b Yellow solid;
ꢀ
1373, 1311, 1237, 1188, 1147, 1111, 1016, 871, 829, 735, 677, 574, 530,
209.3 mg (yield 93%); mp 121e122 C; IR (KBr): 3445, 2382, 2111,
ꢁ1
1
ꢁ1 1
4
68 cm ; H NMR (600 MHz, CDCl
3
):
d
(ppm) 7.66 (d, J¼8.2 Hz, 2H),
1633, 1400, 1227, 1067, 834, 733, 668, 519 cm ; H NMR (600 MHz,
CDCl ):
13
7
CDCl
.24 (d, J¼8.0 Hz, 2H), 5.89 (s, 1H), 2.40 (s, 3H); C NMR (100 MHz,
3
d
(ppm) 7.62 (d, J¼8.6 Hz, 2H), 7.57 (d, J¼8.4 Hz, 2H), 5.92 (s,
1
3
3
)
d
(ppm) 186.0,143.4,134.0,129.2,126.6, 53.7, 21.5; HRMS (ESI):
1H); C NMR (100 MHz, CDCl
3
)
d
(ppm) 185.0, 135.2, 131.8, 128.1,
þ
þ
m/z [MþH] calcd for C
9 9 2 2
H N O : 177.06614; found: 177.06585.
127.5, 54.4; HRMS (ESI): m/z [MþH] calcd for C
8 6 2
H BrN O:
2
24.96574; found: 224.96580.
4
b
4
.5.4. 2-Diazo-1-(4-methoxyphenyl)ethanone (3d). Yellow solid;
ꢀ
165.6 mg (yield 94%); mp 68e69 C; IR (KBr): 3451, 3099, 2933,
4.5.12. 2-Diazo-1-(3-nitrophenyl)ethanone
179.5 mg (yield 94%); mp 147e148 C; IR (KBr): 3447, 3082, 2923,
(3l). Yellow
solid;
ꢀ
2
843, 2107,1608,1511,1460,1420,1368,1308,1262,1236,1176,1116,
ꢁ
1 1
1022, 842, 791, 752, 683, 606, 504 cm ; H NMR (600 MHz, CDCl
3
):
2404, 2186, 2110, 1608, 1531, 1481, 1441, 1376, 1347, 1229, 1141, 1088,
ꢁ
1 1
d
(ppm) 7.74 (d, J¼8.8 Hz, 2H), 6.92 (d, J¼8.8 Hz, 2H), 5.87 (s, 1H),
997, 910, 814, 711, 563, 522, 478 cm ; H NMR (600 MHz, CDCl
3
):
3
.85 (s, 3H); 13C NMR (100 MHz, CDCl
3
)
d
(ppm) 185.1, 163.2, 129.4,
d
(ppm) 8.58 (s,1H), 8.51e8.34 (m,1H), 8.15 (d, J¼7.8 Hz,1H), 7.69 (t,
þ
13
1
C
28.7, 113.7, 55.4, 53.4; HRMS (ESI): m/z [MþH] calcd for
J¼8.0 Hz, 1H), 6.06 (s, 1H); C NMR (100 MHz, CDCl
3
) d (ppm)
H
9 9
N
2
O
2
: 177.06593; found: 177.06585.
183.5, 148.3, 137.8, 132.5, 129.9, 126.9, 121.6, 55.3; HRMS (ESI): m/z
[
MþNa]þ calcd for C
8 5 3 3
H N NaO : 214.0226; found: 214.0223.
4
.5.5. 2-Diazo-1-(3,4-dimethoxyphenyl)ethanone (3e). Yellow solid;
ꢀ
4.5.13. 2-Diazo-1-(4-nitrophenyl)ethanone (3m).4g Yellow solid;
185.6 mg (yield 90%); mp 78e79 C; IR (KBr): 3449, 3064, 2968, 2932,
ꢀ
2
841, 2361, 2110, 1584, 1515, 1455, 1419, 1363, 1266, 1208, 1170, 1143,
183.4 mg (yield 96%); mp 118e119 C;IR(KBr):3447, 3101, 2924,2851,

9326
W.-M. Shu et al. / Tetrahedron 70 (2014) 9321e9329
2
276, 2166, 2114, 1621, 1591, 1518, 1410, 1344, 1216, 1170, 1136, 1104,
2983, 2859, 2756, 1727, 1648, 1606, 1564, 1455, 1389, 1316, 1253,
ꢁ1
1
ꢁ1 1
1
8
012, 844, 708, 553, 513 cm ; H NMR (600 MHz, CDCl
.30 (d, J¼8.4 Hz, 2H), 7.94 (d, J¼9.0 Hz, 2H), 6.04 (s, 1H); C NMR
100 MHz, CDCl (ppm) 184.0,150.0,141.3,127.7,123.8, 55.7; HRMS
3
):
d
(ppm)
1184, 1103, 1023, 903, 856, 758, 627, 560, 515, 478 cm ; H NMR
(600 MHz, CDCl ):
(ppm) 13.13 (s, 1H), 7.99 (d, J¼7.4 Hz, 2H), 7.41
(s, 1H), 7.28 (d, J¼7.8 Hz, 2H), 4.42 (q, J¼7.0 Hz, 2H), 2.41 (s, 3H), 1.38
1
3
3
d
(
(
3
) d
þ
13
ESI): m/z [MþH] calcd for C
8 6 3 3
H N O : 192.04057; found: 192.04037.
(t, J¼7.2 Hz, 3H); C NMR (100 MHz, CDCl
3
) d (ppm) 184.9, 160.9,
1
44.7, 144.3, 141.0, 133.7, 129.8, 129.1, 112.2, 61.4, 21.5, 14.0; HRMS
þ
4.5.14. 2-Diazo-1-(naphthalen-1-yl)ethanone (3n). Yellow solid;
(ESI): m/z [MþH] calcd for C14
15 2 3
H N O : 259.10774; found:
ꢀ
184.4 mg (yield 94%); mp 112e113 C; IR (KBr): 3452, 3109, 2103,
259.10772.
1
618, 1508, 1438, 1397, 1339, 1233, 1179, 1143, 973, 882, 781, 658,
ꢁ
1 1
519 cm ; H NMR (600 MHz, CDCl
3
):
d
(ppm) 8.52 (s, 1H), 7.97 (d,
4.5.21. Ethyl 3-(4-methoxybenzoyl)-1H-pyrazole-5-carboxylate
ꢀ
J¼8.2 Hz, 1H), 7.88 (d, J¼8.2 Hz,1H), 7.64 (d, J¼7.2 Hz,1H), 7.61e7.57
(5ca). Yellow solid; 246.8 mg (yield 90%); mp 109e110 C; IR
13
(
m, 1H), 7.57e7.52 (m, 1H), 7.48 (t, J¼7.8 Hz, 1H), 5.75 (s, 1H);
C
(KBr): 3274, 2986, 2845, 1717, 1647, 1601, 1557, 1510, 1453, 1385,
1385, 1315, 1251, 1194, 1101, 1020, 900, 848, 766, 710, 625, 570, 518,
439 cm ; H NMR (600 MHz, CDCl ): d (ppm) 9.64 (s, 1H), 8.13 (d,
NMR (100 MHz, CDCl (ppm) 189.5, 135.3, 133.7, 131.8, 129.6,
3
) d
ꢁ1 1
1
28.2, 127.4, 126.4, 125.8, 125.3, 124.4, 57.0; HRMS (ESI): m/z
3
þ
[MþH] calcd for C12
H
9
N
2
O: 197.07090; found: 197.07094.
J¼8.2 Hz, 2H), 7.40 (s, 1H), 6.99 (d, J¼8.4 Hz, 2H), 4.44 (q, J¼7.0 Hz,
13
2
H), 3.89 (s, 3H), 1.40 (t, J¼7.0 Hz, 3H); C NMR (100 MHz, CDCl
3
)
4
.5.15. 2-Diazo-1-(naphthalen-2-yl)ethanone (3o). Yellow solid;
d
(ppm) 183.8,164.0,161.0,145.1,141.1,132.2,129.1,113.9,112.0, 61.6,
ꢀ
þ
180.5 mg (yield 92%); mp 51e52 C; IR (KBr): 3447, 3061, 2924,
55.5, 14.2; HRMS (ESI): m/z [MþH] calcd for C14
15 2 4
H N O :
2
8
d
364, 2097, 1607, 1465, 1376, 1275, 1221, 1190, 1121, 1012, 950, 899,
275.10257; found: 275.10263.
ꢁ
1 1
64, 814, 754, 626, 582, 530, 473 cm ; H NMR (600 MHz, CDCl
(ppm) 8.25 (s, 1H), 7.93 (d, J¼8.0 Hz, 1H), 7.91e7.82 (m, 3H),
.63e7.56 (m, 1H), 7.57e7.51 (m, 1H), 6.05 (s, 1H); 13C NMR
3
):
4.5.22. Ethyl 3-(4-chlorobenzoyl)-1H-pyrazole-5-carboxylate
ꢀ
7
(5da). Yellow solid; 239.7 mg (yield 86%); mp 121e123 C; IR
(
1
100 MHz, CDCl
3
)
d
(ppm) 186.1, 135.3, 133.8, 132.4, 129.2, 128.4,
(KBr): 3216, 3092, 2986, 2926, 2861, 2644, 1934, 1723, 1643, 1589,
1466, 1400, 1314, 1258, 1189, 1091, 1028, 1002, 905, 857, 798, 761,
þ
28.1, 127.7, 127.5, 126.7, 122.9, 54.3; HRMS (ESI): m/z [MþNa]
ꢁ1 1
calcd for C12 NaO: 219.0532; found: 219.0529.
8
H N
2
647, 619, 533, 483 cm ; H NMR (600 MHz, CDCl
3
): d (ppm) 12.28
(
s, 1H), 8.09 (d, J¼8.2 Hz, 2H), 7.48 (d, J¼8.4 Hz, 2H), 7.43 (s, 1H),
13
4
.5.16. 2-Diazo-1-(thiophen-2-yl)ethanone
(3p). Yellow
solid;
4.44 (q, J¼7.2 Hz, 2H), 1.41 (t, J¼7.2 Hz, 3H); C NMR (100 MHz,
ꢀ
144.6 mg (yield 95%); mp 59e60 C; IR (KBr): 3450, 3062, 2389, 2291,
CDCl
3
)
d
(ppm) 184.5, 160.4, 146.3, 139.9, 139.7, 134.7, 131.3, 128.8,
þ
2
5
107, 1594, 1516, 1418, 1372, 1241, 1148, 1056, 979, 857, 823, 719, 552,
112.2, 61.8, 14.2; HRMS (ESI): m/z [MþH] calcd for C13
2 3
H12ClN O :
ꢁ
1 1
22 cm ; H NMR (600 MHz, CDCl
3
):
d
(ppm) 7.59 (d, J¼4.9 Hz, 1H),
279.05310; found: 279.05310.
13
7
.54e7.50 (m,1H), 7.12e7.08 (m,1H), 5.86 (s,1H); C NMR (100 MHz,
CDCl (ppm) 178.9,142.4,132.1,129.0,128.0, 54.2; HRMS (ESI): m/z
3
)
d
þ
4.5.23. Ethyl 3-(4-bromobenzoyl)-1H-pyrazole-5-carboxylate
ꢀ
[MþNa] calcd for C
6 4 2
H N ONaS: 174.9939; found: 174.9937.
(5ea). Yellow solid; 294.1 mg (yield 91%); mp 113e115 C; IR
(KBr): 3426, 3218, 2924, 2857, 2643, 1723, 1643, 1584, 1463, 1393,
4
.5.17. 1-(Benzofuran-2-yl)-2-diazoethanone (3q). Yellow solid;
1313, 1255, 1187, 1102, 1067, 1006, 902, 858, 795, 758, 617, 529, 479,
ꢀ
ꢁ1 1
165.7 mg (yield 89%); mp 110e111 C; IR (KBr): 3453, 3114, 3080,
439 cm ; H NMR (600 MHz, CDCl
3
): d (ppm) 12.43 (s, 1H), 8.01 (d,
3
039, 2924, 2111, 1613, 1548, 1474, 1446, 1404, 1282, 1257, 1190,
J¼6.9 Hz, 2H), 7.65 (d, J¼8.2 Hz, 2H), 7.43 (s, 1H), 4.57e4.29 (m,
ꢁ
1
1
13
1034, 944, 862, 740, 599, 524, 430 cm ; H NMR (600 MHz, CDCl
3
):
3
2H), 1.55e1.29 (m, 3H); C NMR (100 MHz, CDCl ) d (ppm) 184.7,
d
(ppm) 7.68 (d, J¼7.9 Hz, 1H), 7.56e7.49 (m, 1H), 7.47e7.46 (m, 1H),
160.4, 146.3, 139.6, 135.1, 131.8, 131.4, 128.6, 112.2, 61.8, 14.2; HRMS
13
þ
7
.45e7.39 (m, 1H), 7.34e7.27 (m, 1H), 6.10 (s, 1H); C NMR
(ESI): m/z [MþH] calcd for C13
2 3
H12BrN O : 323.00254; found:
(
100 MHz, CDCl
3
)
d
(ppm) 176.5, 155.1, 151.8, 127.6, 127.3, 123.8,
323.00258.
þ
1
C
23.0, 112.0, 110.1, 55.1; HRMS (ESI): m/z [MþH] calcd for
H
10 7
N
2
O
2
: 187.05021; found: 187.05020.
4.5.24. Ethyl 3-(4-nitrobenzoyl)-1H-pyrazole-5-carboxylate (5fa).
ꢀ
Yellow solid; 251.6 mg (yield 87%); mp 116e117 C; IR (KBr):
4
.5.18. (E)-1-Diazo-4-phenylbut-3-en-2-one (3r). Yellow solid;
3430, 3230, 3105, 2924, 2859, 1725, 1647, 1601, 1526, 1466, 1406,
1352, 1316, 1258, 1188, 1102, 1021, 909, 851, 797, 733, 617, 532,
ꢀ
156.7 mg (yield 91%); mp 110e111 C; IR (KBr): 3451, 3074, 2104,
ꢁ1 1
1640, 1586, 1495, 1449, 1373, 1200, 1151, 976, 851, 757, 697, 575,
5
473 cm ; H NMR (600 MHz, CDCl
4H), 7.50 (s, 1H), 4.47 (q, J¼7.2 Hz, 2H), 1.44 (t, J¼7.2 Hz, 3H);
NMR (100 MHz, CDCl (ppm) 184.7, 159.6, 150.3, 141.4, 131.1,
123.5, 112.1, 62.1, 14.2; HRMS (ESI): m/z [MþH] calcd for
: 290.07722; found: 290.07715.
3
): d (ppm) 11.83 (s, 1H), 8.35 (s,
ꢁ
1
1
13
04 cm ; H NMR (600 MHz, CDCl
3
):
d
(ppm) 7.60e7.57 (m, 1H),
C
7.54e7.48 (m, 2H), 7.38e7.34 (m, 3H), 6.61e6.59 (m, 1H), 5.48 (s,
1
3
) d
13
þ
H); C NMR (100 MHz, CDCl
3
)
d
(ppm) 184.2, 140.5, 134.2, 130.2,
þ
1
28.8, 128.1, 123.6, 56.1; HRMS (ESI): m/z [MþNa] calcd for
13 12 3 5
C H N O
10 8 2
C H N NaO: 195.0532; found: 195.0529.
4
.5.25. Ethyl 3-(thiophene-2-carbonyl)-1H-pyrazole-5-carboxylate
ꢀ
4
.5.19. Ethyl 3-benzoyl-1H-pyrazole-5-carboxylate (5aa). Yellow
(5ga). Yellow solid; 132.6 mg (yield 53%); mp 122e123 C; IR
(KBr):3457, 3237, 3080, 2978, 2925, 1713, 1623, 1567, 1514, 1464,
1408, 1355, 1264, 1208, 1047, 1018, 992, 800, 745, 616, 513,
ꢀ
solid; 214.9 mg (yield 88%); mp 118e119 C; IR (KBr): 3217, 3065,
2
986, 2927, 2851,1727,1655,1597,1541,1481,1448,1392,1321,1251,
ꢁ1
ꢁ1 1
1
191, 1106, 1026, 992, 903, 849, 776, 733, 695, 620, 579, 514 cm
;
451 cm ; H NMR (600 MHz, CDCl
3
): d (ppm) 11.55 (s, 1H), 8.32 (s,
1
H NMR (600 MHz, CDCl
3
):
d
(ppm) 12.44 (s, 1H), 8.10 (d, J¼7.2 Hz,
1H), 7.76e7.74 (m, 1H), 7.53 (s, 1H), 7.27e7.20 (m, 1H), 4.45 (q,
1
3
2
H), 7.64 (t, J¼7.4 Hz, 1H), 7.52 (t, J¼7.8 Hz, 2H), 7.43 (s, 1H), 4.45 (q,
J¼7.2 Hz, 2H), 1.42 (t, J¼7.2 Hz, 3H); C NMR (100 MHz, CDCl
3
)
1
3
J¼7.2 Hz, 2H), 1.41 (t, J¼7.2 Hz, 3H); C NMR (100 MHz, CDCl
3
)
d
(ppm) 177.3,160.2,147.8,141.7,138.4,135.3,135.1,128.3,111.2, 61.8,
14.1; HRMS (ESI): m/z [MþH] calcd for C11
þ
d
(ppm) 185.4, 160.8, 145.0, 140.9, 136.3, 133.3, 129.7, 128.4, 112.4,
11 2 3
H N O S: 251.04848;
6
2
1.6, 14.1; HRMS (ESI): m/z [MþH]þ calcd for
C
13
H
13
N
2
O
3
:
found: 251.04849.
45.09222; found: 245.09207.
4
.5.26. Ethyl 3-(1-naphthoyl)-1H-pyrazole-5-carboxylate (5ha).
Yellow oil; 229.6 mg (yield 78%); IR (KBr): 3556, 3247, 3058,
2979, 2852, 1727, 1652, 1549, 1508, 1463, 1387, 1312, 1243, 1121,
4
.5.20. Ethyl 3-(4-methylbenzoyl)-1H-pyrazole-5-carboxylate
(5ba). Yellow oil; 224.7 mg (yield 87%); IR (KBr): 3579, 3257,

W.-M. Shu et al. / Tetrahedron 70 (2014) 9321e9329
9327
ꢁ
1
057, 1018, 901, 860, 783, 675, 591, 506, 447 cm 1; 1H NMR
J¼7.0 Hz, 1H), 7.36 (t, J¼7.8 Hz, 1H), 7.17 (d, J¼7.8 Hz, 1H), 3.86 (s,
13
(
400 MHz, CDCl
3
):
d
(ppm) 12.77 (s, 1H), 8.33 (d, J¼9.2 Hz, 1H), 8.00
6
3H); C NMR (100 MHz, DMSO-d ) d (ppm) 187.9, 178.1, 176.0,
(
1
CDCl
1
d, J¼8.2 Hz, 1H), 7.87 (t, J¼6.6 Hz, 2H), 7.64e7.39 (m, 3H), 7.25 (s,
159.4, 146.5, 142.5, 137.3, 134.7, 134.0, 132.9, 130.1, 126.8, 126.6,
13
þ
H), 4.39 (q, J¼7.0 Hz, 2H),1.35 (t, J¼7.0 Hz, 3H); C NMR (100 MHz,
(ppm) 187.1, 160.9, 145.5, 141.9, 134.0, 133.7, 132.7, 130.4,
29.0, 128.4, 127.7, 126.6, 125.1, 124.1, 112.8, 61.5, 14.1; HRMS (ESI):
123.0, 120.4, 113.8, 55.5; HRMS (ESI): m/z [MþNa] calcd for
3
)
d
19 12 2 4
C H N NaO : 355.06904; found: 355.06893.
þ
m/z [MþH] calcd for C17
H
15
N
2
O
3
: 295.10764; found: 295.10772.
4.5.33. 3-(4-Chlorobenzoyl)-1H-benzo[f]indazole-4,9-dione (7da).
ꢀ
Yellow solid; 306.4 mg (yield 91%); mp 264e265 C; IR (KBr):
4
.5.27. Ethyl 3-(2-naphthoyl)-1H-pyrazole-5-carboxylate (5ia).
3454, 3205, 1679, 1647, 1585, 1496, 1382, 1327, 1263, 1208, 1157,
ꢁ
1 1
Yellow oil; 261.9 mg (yield 89%); IR (KBr): 3450, 3255, 3061,
980, 1725, 1647, 1557, 1469, 1391, 1313, 1266, 1233, 1096, 1022, 907,
1091, 1012, 939, 909, 851, 768, 721, 688, 577, 482 cm
(600 MHz, CDCl ): (ppm) 11.84 (s, 1H), 8.28e8.21 (m, 2H), 8.01 (d,
; H NMR
2
8
d
3
d
ꢁ1
1
13
39, 770, 602, 558, 515, 476 cm
;
H NMR (600 MHz, CDCl
3
):
J¼6.0 Hz, 2H), 7.89e7.75 (m, 2H), 7.48 (d, J¼7.8 Hz, 2H); C NMR
(ppm) 12.34 (s, 1H), 8.66 (s, 1H), 8.09 (d, J¼8.6 Hz, 1H), 7.96 (d,
(100 MHz, DMSO-d
6
)
d
(ppm) 186.8, 178.0, 175.9, 139.3, 134.7, 134.0,
þ
J¼8.2 Hz, 1H), 7.93 (d, J¼8.6 Hz, 1H), 7.88 (d, J¼8.2 Hz, 1H), 7.61 (t,
J¼7.4 Hz, 1H), 7.55 (t, J¼7.4 Hz, 1H), 7.48 (s, 1H), 4.45 (q, J¼7.2 Hz,
132.8, 131.7, 128.9, 126.8, 126.6, 120.4; HRMS (ESI): m/z [MþNa]
calcd for C18 ClN NaO : 359.02007; found: 359.01939.
H
9
2
3
13
2
H), 1.41 (t, J¼7.2 Hz, 3H); C NMR (100 MHz, CDCl
3
) d (ppm) 185.3,
160.8,145.6,140.9,135.7,133.7,132.3,131.9,129.7,128.7,128.5,127.7,
4.5.34. 3-(2,4-Dichlorobenzoyl)-1H-benzo[f]indazole-4,9-dione
þ
ꢀ
1
C
26.9, 125.0, 112.4, 61.7, 14.2; HRMS (ESI): m/z [MþH] calcd for
(7ea). Yellow solid; 315.5 mg (yield 85%); mp 214e215 C; IR (KBr):
17
H
15
N
2
O
3
: 295.10763; found: 295.10772.
3453,3249,3068, 2976, 2857, 2361,1678,1586,1555,1473,1405,1376,
1
326,1252,1224,1151,1106,1073,1051,1106,1073, 954, 919, 889, 824,
ꢁ
1 1
4
.5.28. 3-Benzoyl-1H-pyrazole-5-carbonitrile (5ac). White solid;
796, 724, 697 cm ; H NMR (600 MHz, CDCl
3
): d (ppm) 12.68 (s,1H),
ꢀ
132.1 mg (yield 67%); mp 204e205 C; IR (KBr): 3448, 3248, 2957,
8.24 (d, J¼7.4Hz,1H), 8.20(d, J¼7.2Hz,1H), 7.84e7.73 (m, 2H), 7.60 (d,
13
2
7
923, 2853, 2244, 1642, 1445, 1376, 1306, 1210, 1141, 999, 906, 865,
J¼8.2 Hz, 1H), 7.44 (s, 1H), 7.41e7.33 (m, 1H); C NMR (100 MHz,
ꢁ
1 1
97, 730, 689, 614, 491 cm ; H NMR (600 MHz, CDCl
3
):
d
(ppm)
DMSO-d
6
)
d
(ppm) 185.9,177.5,175.8,136.7,136.4,134.7,134.0,132.5,
þ
1
1.83 (s, 1H), 7.97 (d, J¼7.2 Hz, 1H), 7.71 (t, J¼7.6 Hz, 1H), 7.58 (t,
132.3,132.1,130.0,127.6,127.1,126.5,120.3; HRMS (ESI): m/z [MþH]
13
J¼7.8 Hz, 1H), 7.21 (s, 1H); C NMR (100 MHz, DMSO-d
6
) 183.6,
calcd for C18 Cl : 370.99851; found: 370.99847.
H
9
2 2 3
N O
141.3, 135.9, 133.8, 129.4, 128.9, 115.9, 113.7, 109.3; HRMS (ESI): m/z
þ
[MþH] calcd for C11
H
8
N
3
O: 198.06623; found: 198.06619.
4.5.35. 3-(3-Bromobenzoyl)-1H-benzo[f]indazole-4,9-dione (7fa).
ꢀ
Yellow solid; 346.9 mg (yield 91%); mp 248e249 C; IR (KBr):
4
.5.29. 1-(3-Benzoyl-4-phenyl-1H-pyrazol-5-yl)ethanone
3485, 3237, 3065, 1689, 1592, 1496, 1462, 1420, 1382, 1333, 1308,
ꢁ1 1
(5ad). Yellow oil; 223.5 mg (yield 77%); IR (KBr): 3250, 3061, 2921,
1262, 1211, 1163, 1137, 1074, 957, 921, 792, 752, 715, 664 cm ; H
NMR (600 MHz, DMSO-d ): (ppm) 15.46 (s, 1H), 8.30e8.14 (m,
1H), 8.09 (s,1H), 8.09e8.06 (m,1H), 7.95 (d, J¼6.6 Hz, 2H), 7.91e7.85
1
9
d
657, 1600, 1500, 1453, 1421, 1381, 1314, 1279, 1214, 1141, 1074, 1019,
6
d
ꢁ
1 1
49, 908, 744, 697, 613, 563, 512 cm ; H NMR (600 MHz, CDCl
3
):
1
3
(ppm) 12.30 (s, 1H), 7.86 (d, J¼6.4 Hz, 2H), 7.45 (t, J¼7.2 Hz, 1H),
(m, 2H), 7.54 (t, J¼7.8 Hz, 1H); C NMR (100 MHz, DMSO-d
6
)
13
7.30 (s, 7H), 2.29 (s, 3H); C NMR (100 MHz, CDCl
3
)
d
(ppm) 191.4,
d
(ppm) 186.6, 178.0, 175.9, 138.0, 136.8, 134.8, 134.0, 132.8, 132.1,
þ
187.8, 145.8, 142.3, 136.5, 132.9, 130.9, 130.2, 130.1, 128.8, 128.1,
131.1, 129.0, 126.9, 126.6, 122.1, 120.6; HRMS (ESI): m/z [MþH]
þ
1
2
28.0, 127.0, 28.4; HRMS (ESI): m/z [MþH] calcd for C18
H
15
N
2
O
2
:
2 3
calcd for C18H10BrN O : 380.98744; found: 380.98693.
91.11296; found: 291.11280.
4
.5.36. 3-(4-Bromobenzoyl)-1H-benzo[f]indazole-4,9-dione (7ga).
Yellow solid; 362.1 mg (yield 95%); mp 273e275 C; IR (KBr):
ꢀ
4
.5.30. 3-Benzoyl-1H-benzo[f]indazole-4,9-dione
(7aa). Yellow
ꢀ
solid; 272.1 mg (yield 90%); mp 181e183 C; IR (KBr): 3452, 3175,
3205, 3081, 2844, 2362, 1680, 1647, 1580, 1496, 1386, 1327, 1262,
1208, 1153, 1070, 1011, 938, 907, 847, 765, 719, 685, 622, 564,
3
070, 1678, 1644, 1592, 1496, 1452, 1386, 1330, 1263, 1210, 1159,
ꢁ
1
1
ꢁ1 1
;
1
069, 939, 910, 784, 702 cm ; H NMR (600 MHz, CDCl
1.59 (s, 1H), 8.28 (d, J¼6.6 Hz, 1H), 8.24 (d, J¼7.2 Hz, 1H), 8.05 (d,
J¼6.6 Hz, 2H), 7.86e7.74 (m, 2H), 7.66 (t, J¼7.2 Hz, 1H), 7.52 (t,
3
):
d
(ppm)
470 cm
6
H NMR (600 MHz, DMSO-d ): d (ppm) 15.40 (s, 1H),
1
8.28e8.12 (m, 1H), 8.25e8.09 (m, 1H), 7.96e7.88 (m, 3H), 7.87 (s,
13
6
2H), 7.83e7.72 (m, 2H); C NMR (100 MHz, DMSO-d ) d (ppm)
13
J¼7.8 Hz, 2H); C NMR (100 MHz, DMSO-d
6
)
d
(ppm) 188.1, 178.1,
187.1, 178.1, 176.0, 135.0, 134.8, 134.0, 133.9(9), 132.9, 132.0, 131.8,
þ
1
1
76.0, 135.9, 134.7, 134.3, 134.0, 132.9, 129.9, 128.8, 126.8, 126.6,
128.7, 126.9, 126.6, 120.5; HRMS (ESI): m/z [MþH] calcd for
20.3; HRMS (ESI): m/z [MþNa]þ calcd for
C
H
10
N
NaO
:
18
2
3
18 2 3
C H10BrN O : 380.98683; found: 380.98693.
3
4
3
25.05803; found: 325.05836.
4
.5.37. 3-(3-Nitrobenzoyl)-1H-benzo[f]indazole-4,9-dione (7ha).
Yellow solid; 277.8 mg (yield 80%); mp>300 C; IR (KBr): 3486,
ꢀ
.5.31. 3-(4-Methylbenzoyl)-1H-benzo[f]indazole-4,9-dione (7ba).
ꢀ
Yellowsolid;294.2mg(yield93%);mp180e181 C;IR(KBr):3451,
3259, 3082, 1685, 1593, 1532, 1494, 1341, 1262, 1212, 1169, 1137,
ꢁ
1 1
200, 1680, 1641, 1599, 1494, 1384, 1329, 1263, 1210, 1155, 1064, 939,
1091, 970, 925, 856, 714, 668, 564 cm ; H NMR (600 MHz, DMSO-
):
(ppm) 15.46 (s, 1H), 8.70 (s, 1H), 8.56 (d, J¼7.2 Hz, 1H), 8.40 (d,
J¼7.6 Hz, 1H), 8.21e8.10 (m, 1H), 8.10e7.99 (m, 1H), 7.96e7.82 (m,
ꢁ
1 1
9
10, 843, 762, 717, 476 cm ; H NMR (600 MHz, CDCl
1.56 (s, 1H), 8.28 (d, J¼6.2 Hz, 1H), 8.23 (d, J¼6.0 Hz, 1H), 7.93 (d,
J¼7.0 Hz, 2H), 7.80 (t, J¼6.4 Hz, 2H), 7.30 (d, J¼7.2 Hz, 2H), 2.45 (s, 3H);
3
):
d
(ppm)
d
6
d
1
13
6
4H); C NMR (100 MHz, DMSO-d ) d (ppm) 185.7, 177.9, 175.8,
13
C NMR (100 MHz, DMSO-d
6
)
d
(ppm) 187.6,178.2,176.1,145.1,134.7,
147.9, 137.2, 136.1, 134.9, 134.0, 132.7, 130.7, 128.2, 127.0, 126.6, 124.1,
134.0,133.5,133.0, 130.0,129.4,126.8,126.6,120.2, 21.4; HRMS (ESI):
120.8; HRMS (ESI): m/z [MþNa]þ calcd for
18 9 3 5
C H N NaO :
þ
m/z [MþNa] calcd for C19
12 2 3
H N NaO : 339.07395; found: 339.07401.
370.04323; found: 370.04344.
4
.5.32. 3-(3-Methoxybenzoyl)-1H-benzo[f]indazole-4,9-dione
4.5.38. 3-(Thiophene-2-carbonyl)-1H-benzo[f]indazole-4,9-dione
(7ia). Yellow solid; 228.1 mg (yield 74%); mp 276e277 C; IR (KBr):
ꢀ
ꢀ
(7ca). Yellow solid; 305.7 mg (yield 92%); mp 186e187 C; IR (KBr):
3
260, 3077, 1682, 1591, 1550, 1488, 1429, 1383, 1321, 1267, 1215,
3477, 3293, 3083, 1679, 1642, 1589, 1545, 1493, 1410, 1385, 1334,
ꢁ1
1
ꢁ1 1
1150, 1077, 1036, 975, 922, 889, 804, 763, 717, 676, 574 cm
;
H
1267, 1223, 1161, 1136, 1085, 1054, 934, 874, 837, 747, 720 cm ; H
NMR (400 MHz, DMSO-d ): (ppm) 15.38 (s, 1H), 8.25e8.17 (m,
1H), 8.17e8.11 (m, 1H), 8.11e8.02 (m, 1H), 7.96e7.78 (m, 3H),
NMR (600 MHz, CDCl
8
3
):
d
(ppm) 12.40 (s, 1H), 8.25 (d, J¼6.4 Hz,1H),
6
d
.21 (d, J¼7.0 Hz, 1H), 7.86e7.73 (m, 2H), 7.61 (s, 1H), 7.55 (d,

9328
W.-M. Shu et al. / Tetrahedron 70 (2014) 9321e9329
7
.33e7.23 (m, 1H); 13C NMR (100 MHz, DMSO-d
6
)
d
(ppm) 179.4,
7.14 (d, J¼8.6 Hz, 1H), 3.89 (s, 3H), 3.85 (s, 3H); 13C NMR (100 MHz,
1
1
77.8, 175.7, 142.4, 137.2, 134.8, 134.1, 133.9, 132.7, 129.1, 126.9, 126.5,
6
DMSO-d ) d (ppm) 186.8, 153.6, 153.2, 151.1, 148.5, 129.5, 126.3,
20.0; HRMS (ESI): m/z [MþNa]þ calcd for
C
16
H
8
N
NaO
S:
125.9,124.6,122.9,117.0, 115.1, 112.2,110.6, 55.8, 55.5; HRMS (APCI):
2
3
3
4
3
31.01456; found: 331.01478.
m/z [MþH]þ calcd for C19
15 2 5
H N O : 351.09751; found: 351.09755.
.5.39. 3-(2-Naphthoyl)-1H-benzo[f]indazole-4,9-dione (7ja).
4.5.45. 1-(Benzo[d][1,3]dioxole-5-carbonyl)chromeno[3,4-c]pyrazol-
ꢀ
Yellow solid; 324.1 mg (yield 92%); mp 276e277 C; IR (KBr):
4(3H)-one (9da). White solid; 274.1 mg (yield 82%); mp
ꢀ
477, 3293, 3083, 1679, 1642, 1589, 1545, 1493, 1410, 1385, 1334,
268e270 C; IR (KBr): 3448, 3259, 2914, 2361, 1740, 1651, 1606,
ꢁ1 1
1
267, 1223, 1161, 1136, 1085, 1054, 934, 874, 837, 747, 720 cm ; H
NMR (400 MHz, DMSO-d ): (ppm) 15.38 (s, 1H), 8.25e8.17 (m,
H), 8.17e8.11 (m, 1H), 8.11e8.02 (m, 1H), 7.96e7.78 (m, 3H),
.33e7.23 (m, 1H); 13C NMR (100 MHz, DMSO-d
(ppm) 188.1,
78.2,175.7,148.1, 141.4,135.6, 134.8,134.0,133.3,132.9,132.1,129.9,
1500, 1456, 1332, 1276, 1207, 1160, 1099, 1043, 1000, 956, 929, 893,
ꢁ
1 1
6
d
852, 812, 753, 670 cm
8.48 (d, J¼7.8 Hz, 1H), 7.73 (d, J¼8.2 Hz, 1H), 7.59 (s, 1H), 7.57e7.42
; H NMR (400 MHz, DMSO-d ): d (ppm)
6
1
7
1
d
13
6
)
d
(m, 2H), 7.38 (t, J¼7.4 Hz, 1H), 7.10 (d, J¼8.2 Hz, 1H), 6.19 (s, 2H);
C
NMR (100 MHz, DMSO-d (ppm) 186.6, 153.3, 151.9, 151.1, 147.6,
6
) d
1
29.4, 128.6, 127.8, 127.2, 126.9, 126.7, 124.1, 120.5; HRMS (ESI): m/z
143.9, 131.4, 129.5, 127.7, 126.0, 124.6, 123.1, 117.0, 115.3, 109.5, 109.3,
þ
þ
[MþNa] calcd for C22
H
12
N
2
NaO
3
: 375.07401; found: 375.07401.
108.0, 102.2; HRMS (APCI): m/z [MþH] calcd for C18
11 2 5
H N O :
335.06587; found: 335.06625.
4
.5.40. 3-Benzoyl-6,7-dimethyl-1H-benzo[f]indazole-4,9-dione
ꢀ
(7ab). Brown solid; 297.3 mg (yield 90%); mp 262e263 C; IR (KBr):
4.5.46. 1-(4-Chlorobenzoyl)chromeno[3,4-c]pyrazol-4(3H)-one
ꢀ
3
459, 3225, 2919,1675,1598,1541,1502,1450,1379,1329,1258,1176,
(9ea). White solid; 292.2 mg (yield 90%); mp 269e270 C; IR (KBr):
ꢁ
1 1
1059, 1026, 960, 909, 735, 683 cm ; H NMR (400 MHz, DMSO-d
6
):
3454, 3214, 1736, 1661, 1583, 1454, 1425, 1330, 1272, 1205, 1176,
ꢁ1 1
d
(ppm) 15.28 (s, 1H), 8.02e7.86 (m, 3H), 7.82e7.67 (m, 2H), 7.57 (t,
1150, 1114, 1084, 1044, 997, 907, 843, 768 cm ; H NMR (600 MHz,
DMSO-d ): (ppm)
15.61 (s,1H), 8.72 (s,1H), 8.09 (d, J¼7.8 Hz, 2H),
7.68 (d, J¼8.4 Hz, 2H), 7.58 (t, J¼7.8 Hz, 1H), 7.53 (d, J¼8.2 Hz, 1H),
13
J¼7.8 Hz, 2H), 2.39 (s, 3H), 2.37 (s, 3H); C NMR (100 MHz, DMSO-d
(ppm) 188.4, 177.8, 175.1, 147.9, 144.4, 143.3, 140.8, 136.0, 134.1,
31.7, 130.3, 129.9, 128.8, 127.6, 127.3, 120.2, 120.5; HRMS (ESI): m/z
6
)
6
d
d
d
13
1
7.43 (t, J¼7.2 Hz, 1H); C NMR (100 MHz, DMSO-d
6
) d (ppm) 187.3,
þ
[MþH] calcd for C20
H
15
N
2
O
3
: 331.10734; found: 331.10772.
152.8, 151.2, 144.4, 138.2, 136.0, 132.2, 129.8, 128.4, 126.4, 124.6,
1
23.6, 117.0, 114.9; HRMS (APCI): m/z [MþH]þ calcd for
4
.5.41. 3-Benzoyl-1H-naphtho[2,3-f]indazole-4,11-dione
17 2 3
C H10ClN O : 325.03719; found: 325.03745.
ꢀ
(
3
1
4
8
7ac). Yellow solid; 327.6 mg (yield 93%); mp>300 C; IR (KBr):
458, 3200, 3082, 2932, 1676, 1612, 1582, 1548, 1493, 1450, 1399,
322, 1288, 1232, 1178, 1065, 1018, 962, 905, 816, 768, 738, 690, 591,
4.5.47. 1-(Thiophene-2-carbonyl)chromeno[3,4-c]pyrazol-4(3H)-one
ꢀ
(9fa). White solid; 225.2 mg (yield 76%); mp 285e287 C; IR (KBr):
ꢁ
1 1
81 cm
;
H NMR (400 MHz, DMSO-d
6
):
d
(ppm) 15.38 (s, 1H),
3439, 3234, 3111, 1722, 1625, 1513, 1454, 1410, 1356, 1331, 1274,
ꢁ
1
1
.81 (s, 1H), 8.64 (s, 1H), 8.36e8.28 (m, 1H), 8.28e8.14 (m, 1H), 7.98
1205, 1157, 1111, 1046, 1014, 898, 827, 761, 736 cm
(600 MHz, DMSO-d ):
(ppm) 15.63 (s, 1H), 8.82 (d, J¼7.6 Hz, 1H),
8.35e8.31 (m, 1H), 8.18e8.15 (m, 1H), 7.60e7.53 (m, 1H), 7.50 (d,
; H NMR
13
(
(
1
d, J¼7.6 Hz, 2H), 7.87e7.69 (m, 3H), 7.59 (t, J¼7.6 Hz, 2H); C NMR
100 MHz, DMSO-d (ppm) 188.5, 177.6, 175.3, 148.2, 141.9, 136.0,
34.5, 134.3, 134.0, 130.4, 130.1, 130.0, 129.9, 129.7, 129.1, 128.9,
6
d
6
) d
13
J¼8.0 Hz, 1H), 7.42 (t, J¼7.6 Hz, 1H), 7.37e7.33 (m, 1H); C NMR
þ
1
28.9, 121.4; HRMS (ESI): m/z [MþNa] calcd for C22
H
12
N
2
NaO
3
:
(100 MHz, DMSO-d (ppm) 179.1, 152.9, 151.2, 142.0, 136.8, 136.5,
6
) d
375.07457; found: 375.07401.
129.8, 128.6, 126.7, 124.7, 123.3, 117.0, 115.0; HRMS (APCI): m/z
þ
[
MþH] calcd for C15
9 2 3
H N O S: 297.03252; found: 297.03284.
4.5.42. 1-Benzoylchromeno[3,4-c]pyrazol-4(3H)-one (9aa). White
ꢀ
solid; 255.5 mg (yield 88%); mp 257e258 C; IR (KBr): 3424, 3197,
4.5.48. 1-(2-Naphthoyl)chromeno[3,4-c]pyrazol-4(3H)-one (9ga).
ꢀ
2
9
d
361, 1719, 1660, 1454, 1389, 1334, 1275, 1209, 1156, 1115, 1043, 998,
White solid; 309.7 mg (yield 91%); mp 274e275 C; IR (KBr):
ꢁ
1
1
06, 801, 765, 732, 689 cm
;
H NMR (600 MHz, DMSO-d
6
):
3432, 3211, 3110, 3063, 2911, 1734, 1654, 1583, 1461, 1427, 1385,
1331, 1277, 1210, 1179, 1114, 1044, 999, 959, 909, 870, 839, 765, 703,
534 cm ; H NMR (600 MHz, DMSO-d ): d (ppm) 15.56 (s,1H), 8.70
6
(ppm) 15.55 (s, 1H), 8.66 (s, 1H), 8.06 (d, J¼7.2 Hz, 2H), 7.73 (t,
ꢁ
1 1
J¼7.8 Hz, 1H), 7.60 (t, J¼7.8 Hz, 2H), 7.59e7.54 (m, 1H), 7.52 (d,
13
J¼8.4 Hz, 1H), 7.42 (t, J¼7.2 Hz, 1H); C NMR (100 MHz, DMSO-d
6
)
(s, 1H), 8.65 (s, 1H), 8.12 (d, J¼7.8 Hz, 3H), 8.06 (d, J¼8.2 Hz,1H), 7.72
d
(ppm) 188.8, 153.0, 151.2, 137.4, 133.2, 130.4, 129.8, 128.3, 126.2,
(t, J¼7.2 Hz, 1H), 7.65 (t, J¼7.8 Hz, 1H), 7.63e7.51 (m, 2H), 7.43 (t,
þ
13
1
C
24.7, 123.4, 117.0, 115.1; HRMS (APCI): m/z [MþH] calcd for
J¼7.0 Hz, 1H); C NMR (100 MHz, DMSO-d
6
) d (ppm) 188.5, 153.1,
17
H
11
N
2
O
3
: 291.07613; found: 291.07642.
151.2, 135.0,134.6,132.8,131.8,129.7, 128.7,128.0,127.7, 127.0, 126.2,
25.4, 124.7, 123.4, 117.1, 115.1; HRMS (APCI): m/z [MþH] calcd for
þ
1
4
.5.43. 1-(4-Methylbenzoyl)chromeno[3,4-c]pyrazol-4(3H)-one
21 13 2 3
C H N O : 341.09163; found: 341.09207.
ꢀ
(9ba). White solid; 261.7 mg (yield 86%); mp 273e274 C; IR (KBr):
3
434, 3212, 2362, 1736, 1655, 1608, 1455, 1427, 1332, 1275, 1210,
4.5.49. 1-Benzoyl-8-methylchromeno[3,4-c]pyrazol-4(3H)-one
(9ab). White solid; 264.7 mg (yield 87%); mp 258e260 C; IR (KBr):
ꢁ1
1
ꢀ
1
(
180, 1115, 1044, 999, 910, 835, 769, 705, 670 cm
600 MHz, DMSO-d ): (ppm) 15.54 (s, 1H), 8.59 (s, 1H), 7.98 (d,
J¼8.4 Hz, 2H), 7.62e7.54 (m, 1H), 7.54e7.48 (m, 1H), 7.41 (d,
;
H NMR
6
d
3448, 3218, 2362, 1729, 1658, 1435, 1325, 1279, 1208, 1174, 1034,
ꢁ1 1
912, 815, 777, 690 cm
6
; H NMR (600 MHz, DMSO-d ): d (ppm)
13
J¼8.0 Hz, 3H), 2.43 (s, 3H); C NMR (100 MHz, DMSO-d
6
) d (ppm)
15.48 (s, 1H), 8.36 (s, 1H), 8.04 (d, J¼7.4 Hz, 2H), 7.72 (t, J¼7.4 Hz,
13
188.1, 153.2, 151.2, 144.2, 143.8, 134.7, 130.6, 129.6, 129.2, 128.9,
1H), 7.59 (t, J¼7.8 Hz, 2H), 7.40e7.21 (m, 2H), 2.35 (s, 3H); C NMR
(100 MHz, DMSO-d (ppm) 188.7, 153.2, 149.2, 144.1, 137.5, 133.7,
þ
1
26.2, 124.6, 123.2, 117.0, 115.2, 21.3; HRMS (APCI): m/z [MþH]
6
) d
calcd for C18 : 305.09176; found: 305.09207.
H
13
N
2
O
3
133.1, 130.4, 130.3, 129.3, 128.3, 126.1, 123.4, 116.6, 114.8; HRMS
(
APCI): m/z [MþH]þ calcd for C18
13 2 3
H N O : 305.09182; found:
4.5.44. 1-(3,4-Dimethoxybenzoyl)chromeno[3,4-c]pyrazol-4(3H)-one
305.09207.
ꢀ
(9ca). White solid; 283.7 mg (yield 81%); mp 249e250 C; IR (KBr):
3
428, 3228, 2999, 2933, 2838, 1719, 1646, 1592, 1515, 1458, 1333,
Acknowledgements
1
5
8
270, 1236, 1199, 1165, 1140, 1043, 1019, 962, 887, 824, 761, 694,
ꢁ1 1
58 cm
;
H NMR (600 MHz, DMSO-d
6
):
d
(ppm) 15.45 (s, 1H),
We are grateful to the National Natural Science Foundation of
China (Grants 21032001, and 21272085) and the Excellent Doctorial
.49 (s, 1H), 7.77 (s, 1H), 7.66 (s, 1H), 7.59e7.47 (m, 2H), 7.39 (s, 1H),

W.-M. Shu et al. / Tetrahedron 70 (2014) 9321e9329
9329
Dissertation Cultivation Grant from Central China Normal Univer-
sity (No. 2013YBYB61) for financial support. We also thank Dr.
Xiang-Gao Meng for the supporting in X-ray diffraction analysis.
4. For selected reviews, see: (a) Arndt, F.; Eistert, B. Ber. Dtsch. Chem. Ges. 1935, 68,
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2
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Supplementary data
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Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.tet.2014.10.044.
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