Dicopper complexes catalyzed coupling/cyclization of 2-bromobenzoic acids with amidines leading to quinazolinones

Article abstract of DOI:10.1002/aoc.3177

Dicopper(I) complexes {Cu₂(bpnp)(CH₃CN) ₄}(PF₆)₂] (2), [{Cu₂(bpnp)(CH ₃CN)₄}(BAr₄^F)₂] (3) and [Cu₂(bpnp)Cl₂] (4) were prepared from the complexation of [Cu(CH₃CN)₄](PF₆) with 2,7-bis(2-pyridyl)-1,8- naphthyridine (bpnp) followed by anion metathesis and treatment of chloride sequentially. The X-ray structural analysis of 4 indicates the molecule to have a twofold axis passing through the Cu₂Cl₂ core, which has the shape of a butterfly, and that the Cu atom is tetrahedrally coordinated with in a Cl₂N₂ donor set. In preliminary experiments 2 was found to be an effective catalyst in the coupling/cyclization of 2-bromobenzoic acids with amidines, providing the corresponding quinazolinones in good yields. Copyright

Full text of DOI:10.1002/aoc.3177

Full Paper
Received: 21 April 2014
Revised: 15 May 2014
Accepted: 19 May 2014
Published online in Wiley Online Library: 7 July 2014
(wileyonlinelibrary.com) DOI 10.1002/aoc.3177
Dicopper complexes catalyzed coupling/cyclization
of 2-bromobenzoic acids with amidines leading
to quinazolinones
Ming-Uei Hung, Bei-Sih Liao, Yi-Hong Liu, Shie-Ming Peng
and Shiuh-Tzung Liu*
Dicopper(I) complexes {Cu2(bpnp)(CH3CN)4}(PF6)2] (2), [{Cu2(bpnp)(CH3CN)4}(BAr4F)2] (3) and [Cu2(bpnp)Cl2] (4) were
prepared from the complexation of [Cu(CH3CN)4](PF6) with 2,7-bis(2-pyridyl)-1,8-naphthyridine (bpnp) followed by anion
metathesis and treatment of chloride sequentially. The X-ray structural analysis of 4 indicates the molecule to have a
twofold axis passing through the Cu2Cl2 core, which has the shape of a butterfly, and that the Cu atom is tetrahedrally
coordinated with in a Cl2N2 donor set. In preliminary experiments 2 was found to be an effective catalyst in the coupling/
cyclization of 2-bromobenzoic acids with amidines, providing the corresponding quinazolinones in good yields. Copyright
© 2014 John Wiley & Sons, Ltd.
Additional supporting information may be found in the online version of this article at the publisher’s web-site.
Keywords: dimetallic complex; copper; quinazolinones
Introduction
Experimental
General
Quinazolinone derivatives are an important class of heterocy-
clic compounds and its structural motif occurs in many
biological active natural products. These derivatives have
been found in many pharmaceutical applications such as
anti-cancer, anti-bacterial, anti-inflammatory and anti-leukemic
activities.[1] The traditional synthetic approaches leading to
quinazolinones frequently use o-aminobenzoic acid deriva-
tives as the starting materials, which are difficult to prepare.
Today, Ullmann-type N-arylation has become an efficient
route to prepare N-heterocycles.[2] In this regard, Fu and
co-workers reported the synthesis of quinazolinone deriva-
tives from the copper(I)-catalyzed cross-coupling of 2-bromob-
enzaldehyde with acetamidine.[3] A few other Cu-catalyzed
coupling reactions have also been revealed.[4] In spite of these
known catalysts, there is still a need for the development of
more efficient catalytic systems. Few other catalysts involved
Cu catalysis for this coupling reaction.
The use of bimetallic complexes as catalysts in organic
transformations has recently received much attention.[5–9]
Binuclear complexes with metal ions held in close proximity
provide an interaction between metal ions and thus improve
its activity in catalytic reactions. Recently, we have been work-
ing on the development of naphthyridine-based dimetallic
catalysts for C–C and C–N coupling reactions.[8,9] In particular,
the dicopper(II) complex 1 (Scheme 1) was active for oxidative
coupling of phenols and C–N bond formation and its activity
is much better than that of mononuclear species. Herein, we
wish to report the preparation and characterization of
dicopper(I) complexes and their catalytic activity on the
coupling of 2-halobenzoic acid with acetamidine to yield the
corresponding quinazolinone.
All reactions and manipulations steps were performed under an
N2 atmosphere. Dichloromethane and acetonitrile were dried
over CaH2 and distilled under N2. Other chemicals and solvents
were of analytical grade and were used after degassing. The
2,7-bis(2-pyridyl)-1,8-naphthyridine (bpnp) ligand was prepared
according to the method reported previously.[10] NMR spectra
were recorded in CDCl3 or DMSO-d6 on a Bruker Avance 400
spectrometer. Chemical shifts are given in ppm relative to Me4Si
for 1H and 13C NMR. Infrared spectra were measured on a Nicolet
Magna-IR 550 spectrophotometer (Series II).
Preparation of [Cu2(bpnp)(CH3CN)4](BAr4F)2 (3)
A mixture of bpnp (28.4 mg, 0.1 mmol) and [Cu(CH3CN)4PF6] (74.5mg,
0.2 mmol) in anhydrous CH2Cl2 (3 ml) was stirred at room temperature
under N2 for 1 h. The solution turned purple. Sodium tetrakis
(3,5-trifluoromethylphenyl)borate (NaBAr4 ) (177.2 mg, 0.2 mmol)
was added to the above solution. After filtration, the purple solution
was concentrated to give the desired complex as a dark-purple solid
(207 mg, 90%): H NMR (400 MHz, CDCl3): δ 8.46 (d, J=8.0Hz, 2H,
Np–H3), 8.27 (d, J= 8.0 Hz, 2H, Np–H4), 8.14 (d, J= 8.0 Hz, 2H, Py–H3),
7.76–7. 6 (m, 12H, Ar–H), 7.63 (dt, J = 8.0 and 2.0 Hz, 2H, Py-H5),
7.60 (d, J = 8.0 Hz, 2H, Py–H6), 7.08 (dt, J = 8.0 and 2.0 Hz, 2H,
F
1
*
Correspondence to: Shiuh-Tzung Liu, Department of Chemistry, National
Taiwan University, 1, Sec. 4, Roosevelt Road, Taipei, Taiwan 106.
E-mail: stliu@ntu.edu.tw
Department of Chemistry, National Taiwan University, Taipei, Taiwan, 106
Appl. Organometal. Chem. 2014, 28, 661–665
Copyright © 2014 John Wiley & Sons, Ltd.

M.-U. Hung et al.
Scheme 1. Structures of bpnp and Cu(II) complex 1.
Py–H4), 2 (s, 12H, CH3CN). 13C NMR (100 MHz): δ 161 (Ar–C1), 155
(Np–C9), 151 (Np–C2), 149 (Py–C2), 147 (Py–C6), 139 (Np–C4),
Figure 1. ORTEP plot of complex 4 (drawn with 30% probability ellipsoids)
(symmetry operation A: 1x, y, z + 3/2).
1
138 (Py–C4), 135 (Np–C3), 128 (q, JC-F = 268 Hz, –CF3), 127
following obtained compounds have been characterized by com-
paring their 1H and 13C spectral data (see supporting information)
with those reported in the literature:
(Np–C10), 125 (Ar–C2), 123 (Py–C5), 120 (2JC–F = 30 Hz, Ar–C3),
119 (Py–C3), 116 (Ar–C4). Anal. Calcd for C90H48B2Cu2F48N8: C,
46.96; H, 2.10; N, 4.87. Found: C, 46.4; H, 2.36; N, 4.78.
2-Methylquinazolin-4(3H)-one (7aa)[13]
6-Fluoro-2-methylquinazolin-4(3H)-one (7ba)[14]
6-Chloro-2-methylquinazolin-4(3H)-one (7ca)[4]
6-Bromo-2-methylquinazolin-4(3H)-one (7da)[4]
6-Methoxy-2-methylquinazolin-4(3H)-one (7ea)[15]
6,7-Dimethoxy-2-methylquinazolin-4(3H)-one (7fa)[4]
2-Phenylquinazolin-4(3H)-one (7ab)[13]
Preparation of [Cu2(bpnp)Cl2] (4)
A mixture of bpnp (51 mg, 0.18 mmol) and [Cu(CH3CN)4PF6]
(134 mg, 0.36 mmol) in anhydrous CH2Cl2 (5 mL) was stirred at
room temperature under nitrogen atmosphere for 3 h. After
removal of solvent, DMSO (5 ml) and ammonium chloride
(30 mg, 0.56 mmol) were added. The resulting mixture was
heated at 70 °C for 4 h. The solution turned red. Upon cooling
Quinazolin-4(3H)-one (7 ac)[13]
2-Aminoquinazolin-4(3H)-one (7ad)[4]
under nitrogen atmosphere,
a deep-purple solid formed.
Filtration gave the desired complex (81.5 mg, 94%): 1H NMR
(400 MHz, d6-DMSO): δ 8.90 (d, J = 8 Hz, 2H, Np–H3), 8.78 (d,
J = 8.0 Hz, 2H, Np–H4), 8.64 (br, 2H, Py–H6), 8.53 (br, 2 H, Py–H3),
7.99 (t, J = 6.4 Hz, 2H, Py–H4), 7.46 (t, J = 6.4 Hz, 2 H, , Py–H5). 13C
NMR (100 MHz): δ 155.8 (Np–C9), 150.6 (Np–C2), 141.0 (Py–C2),
140.0 (Py–C6), 132.7 (Np–C4), 130.7 (Py–C4), 128.7 (Np–C3),
125.7 (Py–C3), 124.9 (Np–C10), 122.0 (Py–C5). Anal. Calcd for
C18H12Cl2Cu2N4: C, 44.82; H, 2.51; N, 11.62. Found: C, 44.65; H,
2.81; N, 11.59.
Results and Discussion
Preparation and Characterization of Dicopper(I) Complexes
The dicopper complex [Cu2(bpnp)Cl2] (4) could be prepared by
complexation of bpnp with CuCl and characterized by spectroscopic
methods as reported in the literature.[13] However, in this work, we
have developed another approach leading to this complex and
the structure was further confirmed by X-ray crystallography.
Scheme 2 outlines the preparation of complex 4. Starting with
[Cu(CH3CN)4](PF4) as the copper source, complexation with bpnp
proceeded smoothly at ambient temperature. After anion metathe-
sis, complex 3 was isolated as a purple solid in 90% yield. Treatment
of 3 with chloride in DMSO readily gave [Cu2(bpnp)Cl2] as a deep-
purple crystalline solid. Proton NMR data for the complexes showed
that the symmetrical complexes were formed, as only six sets of
ligand signals were found in their 1H NMR spectra (See Experimental
section). Elemental analyses agree with dicopper complexes in which
the atom ratios are in accordance with [Cu2(bpnp)Cl2] (BArF = tetrakis
{3,5-bis(trifluoromethyl)phenyl}borate).
The detailed structure of complex 4 was determined by X-ray
crystallography; an ORTEP plot for the complex is given in Fig. 1.
Complex 4 is comprised of two copper atoms bridged by bpnp
and two chloride ligands, and has crystallographically imposed two-
fold symmetry. The Cu atom has a distorted tetrahedral geometry
defined by the two nitrogen atoms and two bridging chlorides
[Cu1-Cl1 is 2.4746(4) Å and Cu1-Cl1A is 2.3044(4) Å, where A is the
symmetry operation: 1 À x, y, Àz + 3/2]. The copper atom is in a
distorted tetrahedral geometry, being ligated by two nitrogen
atoms of the bpnp ligand. The Cu1-N1 distance [2.090(1) Å] is longer
than that of Cu1–N2 [2.020(1) Å], presumably due to geometrical
constraints of the complex: the bite angle resulting from the chelation
[N1–Cu1–N2 = 79.53(5)°] is much deviated from 90°, which is typical
for pyridinyl-pyrrole ligands. The Cu-Cu distance of 2.6055(4) Å is
much shorter than that of [Cu2(bpnp)(μ-OH)(μ-Cl)Cl2] (3.16 Å)[16]
and [Cu2(bpnp)(μ-OH)(μ-CF3COO) (μ-CF3COO)2] (3.09 Å).[10]
Crystallography
Crystals suitable for X-ray determination were obtained for complex
4 by recrystallization from methanol/ether at room temperature.
Measurements were made on an Oxford Diffraction Gemini A diffrac-
tometer. Crystal data: C18H12Cl2Cu2N4, Fw = 482.30, T=150(2) K,
monoclinic, C2/c, a= 15.3069(4) Å, b= 8.8743(2) Å, c= 12.3694(2) Å,
β = 91.469(2)°, V= 1679.68(6) Å3, Z=4, Dcalcd = 1.907 Mg mÀ3, F
(000) = 960, crystal size: 0.10 × 0.15 × 0.20 mm3, θ range: 3.1–27.5°,
19 018 reflections collected, 1930 unique reflections (Rint =0.022)
and 1800 with I≥2σ(I). Final R indices: R1 = 0.020, wR2= 0.055
(obs. data); R1 = 0.022, wR2 = 0.056 (all data). GoF on F2 = 1.01. Data
processing was with the standard software.[11] The structure was
solved and refined in the standard mode with SHELXS97 and
SHELXL97,[12] and Fig. 1 was drawn with ORTEP.[12]
General Procedure for Cu(I) Catalysis
A mixture of 2-bromobenzoic acid (0.50 mmol), amidine hydrochlo-
ride (0.75 mmol),Cs2CO3 (3.0mmol, 489 mg) and Cu complex in pre-
dried DMF (2ml) was placed in a sealed reaction tube. The reaction
mixture was stirred at 70 °C for 12 h. After completion of the
reaction, a brine solution (30 ml) was added and extracted with
ethyl acetate (30 × 3 ml). The organic extracts were dried over
MgSO4 and concentrated. The residue was chromatographied on
a silica gel column with elution of hexane/ethyl acetate. The
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Appl. Organometal. Chem. 2014, 28, 661–665

Formation of quinazolinones catalyzed by a dicopper complex
best yield. It is worth noting that the reaction proceeded very
efficiently in DMF. Next, a series of trial reactions in the presence
of various copper complexes were conducted to compare the
activity of these pre-catalysts (entries 7–13). On the basis of
product analysis, all copper complexes have good activity in the
coupling/cyclization of 2-bromobenzoic acids with amidines.
Among these copper catalysts, dicopper complexes prove to
have better activity, whereas mononuclear copper complexes
show moderate activity.
To further validate the activity of the dicopper system 2, the
product distribution of reaction of 2-bromobenzoic acid with
acetamidine catalyzed by 2 and [{Cu(CH3CN)4}(PF6)] was moni-
tored by NMR spectroscopy. The results showed that the
reaction catalyzed by 2 is faster by ~50% than that catalyzed
by [{Cu(CH3CN)4}(PF6)]. This observation indicates that the
dicopper system has an enhanced activity in comparison to
the monocopper complex. This might be due to a cooperative
effect between two metal centers in the dicopper system,
which is absent in a mononuclear species. Further evidence
to support this was the observation of mass fragment [Cu2(bpnp)
(μ-OH)(OH)2]+ (m/z found 460.95, calcd 460.28) from the
catalytic mixture.
Scheme 2. Preparation of dicopper(I) complexes.
In view of the above results, we explored other substrates
under this catalytic condition. This method is also applicable to
various substituted 2-bromobenzoic acids and amidines, as illus-
trated in Table 2. Generally, 2-bromobenzoic acids containing an
electron- withdrawing or -donating group on the phenyl ring
afforded the corresponding product in good to excellent yields
(Table 2, entries 1–6). It was noticed that the reaction of 2,
5-dibromobenzoic acid with acetamidine gave quinazolinone
7da in 77% yield, in which the bromo group at the 5-position
remained intact, i.e. no reaction on this moiety. However, the
substituent effect on the amidines is quite substantial. Pyrazole-
1-carboxamidine (6e) and formamidinesulfinic acid (6f) did not
undergo the expected reaction due to the decomposition of
substrates under the catalytic conditions.
Catalysis
With the dicopper(I) complexes in hand, their catalytic activities
toward the coupling of 2-halobenzoic acid with acetamidine
leading to quinazolinone were investigated. To obtain informa-
tion on the catalytic system, we first examined the reaction by
dicopper complexes in the presence of various bases or solvents
(Table 1). Typically, a mixture of 2-bromobenzoic acid (0.5 mmol),
acetamidine hydrochloride (0.75 mmol) and base (1.5 mmol) in
DMF (2 ml) was heated under N2 atmosphere at 70 °C for 6 h.
The product was isolated by chromatography and identified by
1H NMR spectroscopy. The results are summarized in Table 2. It
appears that the bases affect the formation of product dramati-
cally. Various bases do assist the reactions, but Cs2CO3 gives the
Table 1. Coupling of 2-iodobenzoic acid with acetamidine leading to quinazolinonea
Entry
Catalyst
Base
Solvent
Yield (%)b
1
2 (2 mol%)
2 (2 mol%)
2 (2 mol%)
2 (2 mol%)
2 (2 mol%)
2 (2 mol%)
2 (2 mol%)
2 (2 mol%)
—
Cs2CO3
Cs2CO3
Cs2CO3
K2CO3
KOH
DMF
THF
90
86c
17
57
52
48
23
15
0
2
3
H2O
DMF
DMF
4
5
6
NaOH
7
Pyridine
Et3N
8
9
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
10
11
12
13
14
15
16
3 (2 mol%)
85
84
78
53
56
44
78
[Cu2(bpnp)(Cl)2] (4) (2 mol%)d
[Cu(CH3CN)4](PF6) (4 mol%)
[Cu(CH3CN)4](PF6) + bpy (4 mol%)d
[Cu(CH3CN)4](PF6) + TMEDA (4 mol%)d
CuI (4 mol%)
Cu(OAc)2 (5 mol%)
aReaction conditions: 2-bromobenzoic acid (0.5 mmol), acetamidine hydrochloride (0.75 mmol) and base (1.5 mmol) in
solvent (2 ml) was heated at 70 °C for 6 h under N2 atmosphere.
bIsolated yield.
c20 h.
dbpnp = 2,7-bis(2-pyridyl)-1,8-naphthyridine, bpy = bipyridine, TMEDA = tetramethylethylenediamine.
Appl. Organometal. Chem. 2014, 28, 661–665
Copyright © 2014 John Wiley & Sons, Ltd.
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M.-U. Hung et al.
Table 2. Formation of quinazolinones catalyzed by dicopper complex 2a
Entry
R
R′
Product
Yieldb
1
H (5a)
CH3 (6a)
CH3 (6a)
CH3 (6a)
CH3 (6a)
CH3 (6a)
CH3 (6a)
Ph (6b)
H (6c)
7aa, R = H; R′ = Me
7ba, R = F; R′ = Me
7ca, R = Cl; R′ = Me
7da, R = Br; R′ = Me
7ea, R = MeO; R′ = Me
7fa, R = 5,6-(MeO)2; R′ = Me
7ab, R = H; R′ = Ph
7 ac, R = H; R′ = H
7ad, R = H; R′ = NH2
—
87%
93%
80%
77%
98%
79%
99%
41%
66%
2
5-F (5b)
5-Cl (5c)
3
4
5-Br (5d)
5-MeO (5e)
5,6-(MeO)2 (5f)
H (5a)
5
6
7
8c
9c
10
H (5a)
H (5a)
NH2 (6d)
c
H (5a)
—
(6e)
c
11
H (5a)
SO2H (6f)
—
—
aReaction conditions: 2-bromobenzoic acid (0.5 mmol), amidine hydrochloride (0.75 mmol), catalyst (0.01 mmol),
Cs2CO3 (1.5 mmol) in DMF (2 ml), 70 °C, 6 h, under N2 atmosphere.
bIsolated yield.
cStarting material decomposed.
dTHF as solvent.
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A new catalytic system for the coupling followed by cyclization of
2-bromobenzoic acid with amidine leading to the corresponding
quinazolinone has been developed in this work. The activity of
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Appl. Organometal. Chem. 2014, 28, 661–665
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