Palladium-Catalyzed Oxidative Direct ortho-C-H Acylation of Arenes with Aldehydes under Aqueous Conditions

Article abstract of DOI:10.1002/ejoc.201501187

Palladium-catalyzed ortho-acylation of arenes with aldehydes in the presence of tert-butyl hydroperoxide (TBHP) as the oxidant under aqueous conditions has been demonstrated. The acylation reaction exhibits excellent regioselectivity and wide functional g

Full text of DOI:10.1002/ejoc.201501187

FULL PAPER
DOI: 10.1002/ejoc.201501187
Palladium-Catalyzed Oxidative Direct ortho-C–H Acylation of Arenes with
Aldehydes under Aqueous Conditions
Fuhong Xiao,*[a] Shuqing Chen,[a] Huawen Huang,[a] and Guo-Jun Deng*[a]
Keywords: Palladium / Aldehydes / Oxidation / Acylation / Green chemistry / Regioselectivity
Palladium-catalyzed ortho-acylation of arenes with alde- strated. The acylation reaction exhibits excellent regioselec-
hydes in the presence of tert-butyl hydroperoxide (TBHP) as
tivity and wide functional group tolerance.
the oxidant under aqueous conditions has been demon-
neat conditions.[4b] In 2010, Yu and co-workers utilized ox-
imes as a directing group for direct C–H bond acylation,
cross-coupling aromatic oximes and aldehydes in toluene.[5a]
In 2011, the groups of Yu, Kwong, Wang, and Li indepen-
dently published their results on the acylation of anilides
with aldehydes.[6] Besides aldehydes, we found that alcohols
could also be used as efficient acylating reagents through in
situ oxidation.[12]
However, most of the procedures described above were
carried out in organic solvents. From the perspective of
green chemistry, water is a desirable solvent for chemical
transformation because of its natural, inexpensive, non-
toxic, and environmentally friendly character.[13] During the
last few years, occasional examples of acylation with alde-
hydes in water have been reported. In 2013, Novák and co-
workers further improved the acylation of anilides with aro-
matic aldehydes. Good to excellent yields of the desired
products were obtained under aqueous conditions.[14a] In
spite of this, direct acylation of arenes with aldehydes is
still very little exploited. Here we wish to describe a new
palladium-catalyzed sp2 C–H activation reaction for the
synthesis of aryl ketones from aldehydes with use of water
as the sole solvent. The utilization of aqueous media and
anionic surfactants enables high efficiency of this transfor-
mation through “on water” effect catalysis[15] (Scheme 1).
Introduction
Diaryl ketones are fundamental building blocks in the
synthesis of pharmaceuticals, natural products, functional
materials, and agrochemicals.[1] The traditional methods for
the synthesis of aryl ketones mainly rely on Friedel–Crafts
acylation of arenes in the presence of Lewis acids or on
oxidation of the corresponding secondary alcohols.[2] In re-
cent years, great efforts have been paid to the development
of direct acylation without the use of acids.[3]
Transition-metal-catalyzed oxidative acylations of aro-
matic sp2 C–H bonds in proximity to various directing
groups – such as pyridines,[4] oximes,[5] anilides,[6] indole,[7]
2-arylbenzoxazoles,[8] N-benzyltriflamides,[9] azoxybenz-
enes,[10] and others[11] – with aldehydes have been success-
fully exploited (Scheme 1). For example, in 2009, Cheng re-
ported the first example of palladium-catalyzed acylation
of 2-arylpyridines through ortho-C–H bond activation with
aldehydes to give diaryl ketones in dry xylene.[4a] Shortly
afterwards, Li found that both aromatic and aliphatic alde-
hydes could be successfully applied in this reaction under
Results and Discussion
In our initial study, acetophenone O-methyl oxime (1a)
and benzaldehyde (2a) were chosen as model substrates for
optimization of the reaction conditions, and selected results
are summarized in Table 1. To our delight, a 22% yield of
the desired product was obtained in the presence of 5 mol-
% PdCl2 and 2 equiv. of tert-butyl hydrogen peroxide
(TBHP) in H2O at 50 °C after 12 h (Entry 1). To improve
the solubility of the reactants in water, 5 mol-% sodium do-
decylsulfate (SDS) was added to the system. Various palla-
dium catalysts including Pd(OAc)2, Pd(CH3CN)Cl2, and
Pd(acac)2 were examined (Entries 3–5), and of them
Scheme 1. C–H bond acylation with aldehydes.
[a] Key Laboratory for Environmentally Friendly Chemistry and
Application, Ministry of Education, College of Chemistry,
Xiangtan University,
Xiangtan 411105, P. R. China
E-mail: fhxiao@xtu.edu.cn
gjdeng@xtu.edu.cn
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201501187.
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F. Xiao, S. Chen, H. Huang, G.-J. Deng
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Pd(OAc)2 was found to be most effective in this coupling Table 2. Reactions between acetophenone O-methyl oxime and
aldehydes.[a]
reaction. Variation of the phase-transfer catalysts showed
that SDS is superior to other phase-transfer catalysts such
as TBAB, TBAI, SDBS (sodium dodecylbenzenesulfonate),
18-C-6 (18-crown-6), or dibenzo-18-crown-6 (Entries 6–11).
A screening of oxidants showed that TBHP gave the best
result, with TBP (tert-butyl peroxide), BQ, CHP (cumene
hydroperoxide), and O2 being found to be inferior (En-
tries 12–15).
Table 1. Optimization of the reaction conditions.[a]
[a] Conditions: 1a (0.4 mmol), 2 (1 mmol), Pd(OAc)2 (5 mol-%),
SDS (5 mol-%), TBHP (2.0 equiv.), 50 °C, 12 h, H2O (0.6 mL), air.
[b] Isolated yield.
Table 3. Reactions between 2-phenylpyridine and aldehydes.[a]
[a] Conditions: 1a (0.4 mmol), 2a (1 mmol), Pd(OAc)2 (5 mol-%),
SDS (5 mol-%), TBHP (2.0 equiv.), 50 °C, 12 h, H2O (0.6 mL), air.
[b] GC yield.
A variety of substituted aromatic aldehydes were treated
with acetophenone O-methyl oxime (1a) under the opti-
mized conditions (Table 2). In general, aromatic aldehydes
containing either electron-withdrawing or -donating groups
on the aromatic ring all coupled efficiently with aceto-
phenone O-methyl oxime to give the desired acylated prod-
ucts in moderate to good yields. Aldehydes 2b, 2c, and 2g,
with para-substituted electron-donating groups [Me, OMe,
and C(CH3)3], gave the corresponding products 3b, 3c, and
3g in high yields (Entries 2, 3, and 7). A slightly lower yield
was obtained when 4-fluorobenzaldehyde (2d) was used, the
desired product being produced in 53% yield (Entry 4).
Moderate to good yields were achieved when 2-chlorobenz-
aldehyde, 3-methylbenzaldehyde, and 2-naphthaldehyde
were used (Entries 8–10).
Furthermore, we examined the reactions between 2-
phenylpyridine and various substituted aldehydes (Table 3).
[a] Conditions: 6a (0.4 mmol), 2 (1 mmol), Pd(OAc)2 (5 mol-%),
SDS (5 mol-%), TBHP (2.0 equiv.), 50 °C, 12 h, H2O (0.6 mL), air.
We reoptimized the reaction conditions and were delighted [b] Isolated yield.
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Pd-Catalyzed ortho-C–H Acylation under Aqueous Conditions
to find that the reactions could be smoothly performed at pound 1d) groups on the phenyl ring afforded the desired
80 °C, with the desired product 5a, for example, being af- products in moderate to good yields (Entries 1–3). Propio-
forded in 78% yield (Entry 1). The directed acylation of 2- phenone O-methyl oxime (1e) and benzaldehyde O-methyl
phenylpyridine with various aldehyde derivatives was con- oxime (1f) were also reactive toward benzaldehyde and gave
ducted under the optimized reaction conditions. In general, the desired products in 67% and 53% yields (Entries 4 and
reactions between 2-phenylpyridine and the aldehyde deriv- 5). Likewise, effective transformation of the tetralone ana-
atives either with electron-donating groups [such as CH3, logue 1g was also accomplished with benzaldehyde as the
OCH3, or C(CH3)3] or with electron-withdrawing groups coupling partner (Entry 6). Moreover, 2-arylpyridines and
(such as F, Cl, or Br) on the aromatic ring gave moderate aromatic azo compounds were employed to react with 2a
to good yields. The positions of the substituents on the under the optimized conditions (Entries 7–11). When
benzaldehyde phenyl ring significantly affected the reaction benzo[h]quinoline (4e) was applied in the system, an 85%
yields, and the use of 2-chlorobenzaldehyde resulted in yield of the acylation product was isolated (Entry 10).
product 5h in only 58% yield (Entry 8).
Subsequently, diphenyldiazene was employed for trans-
formations of this kind with various aldehydes. These re-
sults are shown in Table 4. In general, aldehydes possessing
electron-withdrawing groups (such as F, Cl, or Br) on the
phenyl ring gave higher yields than those with electron-do-
nating groups (such as CH3, OCH3). The positions of the
substituents on the benzaldehyde phenyl ring also signifi-
cantly affected the reaction yields, and the use of 2-chloro-
benzaldehyde resulted in product 7g in only 53% yield (En-
try 7).
Table 5. Different directing groups for the synthesis of ketones.[a]
Table 4. Reactions between diphenyldiazene and aldehydes.[a]
[a] Conditions: 1 (0.4 mmol), 2a (1 mmol), Pd(OAc)2 (5 mol-%),
SDS (5 mol-%), TBHP (2.0 equiv.), 50 °C, 12 h, H2O (0.6 mL), air.
[b] Isolated yield. [c] 50 °C. [d] 80 °C. [e] 100 °C.
[a] Conditions: 6a (0.4 mmol), 2 (1 mmol), Pd(OAc)2 (5 mol-%),
SDS (5 mol-%), TBHP (2.0 equiv.), 50 °C, 12 h, H2O (0.6 mL), air.
[b] Isolated yield.
On the basis of previous studies and our observations, a
possible mechanism for the reaction is illustrated
To expand the scope of this direct acylation reaction fur- (Scheme 2). The palladium catalyst could react with I to
ther, we next investigated direct C–H bond acylation by form a cyclopalladated intermediate A by chelation-directed
cross-coupling of benzaldehyde (2a) with aryl ketone ox- C–H activation, as has been confirmed in many related re-
imes, 2-arylpyridines, and aromatic azo compounds, with ports.[4b,5a,16] The PdII intermediate A could then react with
the results shown in Table 5. The initial investigations were the acyl radical, generated in situ by hydrogen atom ab-
focused on reactions between ketone oximes and benzalde- straction from the aldehyde, to afford the PdIV or dimeric
hyde. All of the aryl ketone oximes bearing electron-donat- PdIII intermediates B through oxidative addition. Finally,
ing (compounds 1b, 1c) or electron-withdrawing (com- intermediates B could undergo reductive elimination to
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F. Xiao, S. Chen, H. Huang, G.-J. Deng
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generate the acylation product, and PdII would be regener-
ated for the next catalytic cycle.
troleum ether/ethyl acetate 9:1) to give 3a as a pale yellow solid;
yield: 71 mg (70%).
{2-[1-(Methoxyimino)ethyl]phenyl}(phenyl)methanone (3a):[17] CAS
1
number 1401733-54-7. H NMR (CDCl3, 400 MHz): δ = 7.71 (d,
J = 7.4 Hz, 2 H), 7.52–7.48 (m, 5 H), 7.42–7.38 (m, 2 H), 3.68 (s,
3 H), 2.03 (s, 3 H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 197.4,
153.9, 138.9, 138.2, 136.4, 132.4, 130.1, 129.3, 128.9, 128.5, 128.1,
127.6, 61.6, 14.3 ppm. MS (EI): m/z (%) = 253, 222, 208, 152, 77.
{2-[1-(Methoxyimino)ethyl]phenyl}(p-tolyl)methanone (3b):[17] CAS
1
number 1401733-58-1. White solid, yield 76%. H NMR (CDCl3,
400 MHz): δ = 7.62 (d, J = 8.0 Hz, 2 H), 7.52–7.48 (m, 2 H), 7.45–
7.44 (m, 2 H), 7.20 (d, J = 7.9 Hz, 2 H), 3.69 (s, 3 H), 2.40 (s, 3
H), 2.03 (s, 3 H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 197.3,
154.1, 143.3, 139.2, 136.4, 135.6, 130.0, 129.6, 129.0, 128.9, 128.5,
127.7, 61.7, 21.7, 14.5 ppm. MS (EI): m/z (%) = 267, 236, 222, 119,
91.
{2-[1-(Methoxyimino)ethyl]phenyl}(4-methoxyphenyl)methanone (3c,
1
CAS 1401733–61–6):[17] White solid, yield 75%. H NMR (CDCl3,
400 MHz): δ = 7.71 (d, J = 8.7 Hz, 2 H), 7.50–7.44 (m, 4 H), 6.89
(d, J = 8.7 Hz, 2 H), 3.86 (s, 3 H), 3.70 (s, 3 H), 2.04 (s, 3 H) ppm.
13C NMR (CDCl3, 100 MHz): δ = 196.3, 163.2, 154.2, 139.2, 136.4,
131.8, 130.1, 129.9, 128.7, 128.4, 127.8, 113.5, 61.7, 55.4, 14.7 ppm.
MS (EI): m/z (%) = 283, 252, 238, 135, 77.
Scheme 2. Proposed mechanism.
(4-Fluorophenyl){2-[1-(methoxyimino)ethyl]phenyl}methanone (3d):
Pale yellow solid, yield 53%. 1H NMR (CDCl3, 400 MHz): δ =
7.75–7.72 (m, 2 H), 7.56–7.45 (m, 4 H), 7.10–7.05 (m, 2 H), 3.66
(s, 3 H), 2.04 (s, 3 H) ppm. 13C NMR (CDCl3, 100 MHz): δ =
196.0, 165.4 (d, J = 253 Hz), 153.8, 138.7, 136.2, 134.7 (d, J =
3.2 Hz), 131.8 (d, J = 9.2 Hz), 130.2, 128.7, 128.6, 127.7, 115.4 (d,
J = 21.8 Hz), 61.7, 14.3 ppm. MS (EI): m/z (%) = 271, 240, 226,
123, 95. HRMS calcd. for C16H15FNO2 [M + H]+ 272.1081; found
272.1081.
Conclusions
In summary, a highly efficient, environmentally benign,
and regioselective synthetic method for the synthesis of di-
aryl ketones has been developed. The reactions took place
at mild temperature, in water as the solvent. Halogen and
other functional groups were well tolerated under the opti-
mized reaction conditions. This method affords an alterna-
tive approach for the synthesis of biologically important di-
aryl ketones.
(4-Chlorophenyl){2-[1-(methoxyimino)ethyl]phenyl}methanone
(3e):[5a] CAS number 1240389-12-1. White solid, yield 78 %. 1H
NMR (CDCl3, 400 MHz): δ = 7.65 (d, J = 8.44 Hz, 2 H), 7.56–
7.43 (m, 4 H), 7.37 (d, J = 8.5 Hz, 2 H), 3.67 (s, 3 H), 2.05 (s, 3
H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 196.1, 153.5, 138.7,
136.6, 131.8, 130.5, 130.2, 129.3, 128.7, 128.6, 128.5, 127.6, 61.6,
14.1 ppm. MS (EI): m/z (%) = 287, 256, 152, 111, 75.
(4-Bromophenyl){2-[1-(methoxyimino)ethyl]phenyl}methanone
(3f):[5b] Pale yellow solid, yield 72%. 1H NMR (CDCl3, 400 MHz):
δ = 7.58–7.43 (m, 8 H), 3.70 (s, 3 H), 2.05 (s, 3 H) ppm. 13C NMR
(CDCl3, 100 MHz): δ = 196.3, 153.5, 138.3, 137.0, 136.0, 131.5,
130.6, 130.2, 128.7, 128.6, 127.5, 127.4, 61.6, 14.0 ppm. MS (EI):
m/z (%) = 331, 300, 286, 154, 76.
Experimental Section
General Methods: All experiments were carried out under air. Flash
column chromatography was performed over silica gel (48–75 μm).
1H NMR and 13C NMR spectra were recorded with a Bruker-AV
(400 and 100 MHz, respectively) instrument internally referenced
to SiMe4 or chloroform signals. MS analyses were performed with
an Agilent 5975 GC–MS instrument (EI). High-resolution mass
spectra were recorded at the Center for Mass Spectrometry, Peking
University. The structures of known compounds were further cor-
roborated by comparing their 1H NMR spectroscopic data and MS
data with those in the literature. All reagents were used as received
from commercial sources without further purification.
[4-(tert-Butyl)phenyl]{2-[1-(methoxyimino)ethyl]phenyl}methanone
1
(3g): Pale yellow solid, yield 75%. H NMR (CDCl3, 400 MHz): δ
= 7.67 (d, J = 8.06 Hz, 2 H), 7.50 (s, 2 H), 7.44–7.41 (m, 4 H), 3.70
(s, 3 H), 2.04 (s, 3 H), 1.34 (s, 9 H) ppm. 13C NMR (CDCl3,
100 MHz): δ = 197.1, 156.2, 154.2, 139.0, 136.5, 135.3, 129.9, 129.4,
128.8, 128.3, 127.8, 125.1, 61.5, 35.0, 31.1, 14.6 ppm. MS (EI): m/z
(%) = 309, 278, 176, 117, 57. HRMS calcd. for: C20H24NO2 [M +
H]+ 310.1801; found 310.1801.
General Procedure – Compound 3a: A 10 mL oven-dried reaction
vessel was charged with acetophenone O-methyl oxime (1a, 70 μL,
0.4 mmol), benzaldehyde (2a, 100 μL, 1.0 mmol), tert-butyl hydro-
peroxide (115 μL, 0.8 mmol), palladium acetate (4.5 mg, 5 mol-%),
and sodium dodecylsulfate (5.8 mg, 5 mol-%). H2O (0.6 mL) was
added to the sealed reaction vessel by syringe. The resulting solu-
tion was stirred at 50 °C for 12 h. After the mixture had cooled to
room temperature the volatiles were removed under vacuum and
the residue was purified by column chromatography (silica gel, pe-
(2-Chlorophenyl){2-[1-(methoxyimino)ethyl]phenyl}methanone (3h):
Pale yellow solid, yield 57%. 1H NMR (CDCl3, 400 MHz): δ =
7.56 (t, J = 8.12 Hz, 2 H), 7.47–7.39 (m, 5 H), 7.30–7.26 (m, 1 H),
3.88 (s, 3 H), 1.99 (s, 3 H) ppm. 13C NMR (CDCl3, 100 MHz): δ
= 195.5, 155.8, 138.2, 138.1, 137.8, 132.4, 131.8, 131.5, 131.0, 130.6,
130.4, 128.6, 128.5, 126.3, 61.7, 15.3 ppm. MS (EI): m/z (%) = 287,
256, 152, 111, 75. HRMS calcd. for: C16H15ClNO2 [M + H]+
288.0785; found 288.0785.
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Pd-Catalyzed ortho-C–H Acylation under Aqueous Conditions
{2-[1-(Methoxyimino)ethyl]phenyl}(m-tolyl)methanone (3i):[5b] Pale
[4-(tert-Butyl)phenyl][2-(pyridin-2-yl)phenyl]methanone (5g): White
yellow solid, yield 80%. 1H NMR (CDCl3, 400 MHz): δ = 7.55– solid, yield 75%. 1H NMR (CDCl3, 400 MHz): δ = 8.40 (d, J =
7.47 (m, 6 H), 7.34–7.26 (m, 2 H), 3.70 (s, 3 H), 2.37 (s, 3 H), 2.02
(s, 3 H) ppm. 13C NMR (CDCl3, 100 MHz): δ = δ = 197.6, 154.1,
138.9, 138.1, 137.9, 136.5, 133.2, 130.1, 129.7, 128.9, 128.4, 128.0,
127.6, 126.6, 61.5, 21.2, 14.4 ppm. MS (EI): m/z (%) = 267, 236,
222, 176, 91.
4.36 Hz, 1 H), 7.76 (d, J = 7.68 Hz, 1 H), 7.65–7.46 (m, 7 H), 7.30
(d, J = 8.4 Hz, 2 H), 7.02 (t, J = 5.98 Hz, 1 H), 1.27 (s, 9 H) ppm.
13C NMR (CDCl3, 100 MHz): δ = 197.8, 157.0, 156.0, 149.1, 139.7,
139.6, 136.1, 135.1, 130.0, 129.6, 128.9, 128.89, 128.2, 124.9, 122.8,
121.7, 34.9, 31.0 ppm. MS (EI): m/z (%) = 315, 286, 182, 127, 77.
HRMS calcd. for: C22H22NO [M + H]+ 316.1695; found 316.1694.
{2-[1-(Methoxyimino)ethyl]phenyl}(naphthalen-2-yl)methanone (3j):
1
(2-Chlorophenyl)[2-(pyridin-2-yl)phenyl]methanone (5h):[12] CAS
Yellow solid, yield 77%. H NMR (CDCl3, 400 MHz): δ = 8.08 (s,
1
1 H), 7.96–7.82 (m, 4 H), 7.59–7.50 (m, 6 H), 3.63 (s, 3 H), 2.02 (s,
3 H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 197.4, 154.0, 138.9,
136.5, 135.5, 135.3, 132.3, 131.0, 130.1, 129.3, 129.0, 128.5, 128.14,
128.12, 127.7, 127.68, 126.5, 124.9, 61.5, 14.3 ppm. MS (EI): m/z
(%) = 303, 272, 202, 127, 77. HRMS calcd. for: C20H18NO2 [M +
H]+ 304.1332; found 304.1332.
Phenyl[2-(pyridin-2-yl)phenyl]methanone (5a):[12] CAS number
198478-48-7. White solid, yield 78%. 1H NMR (CDCl3, 400 MHz):
δ = 8.50 (d, J = 4.36 Hz, 1 H), 7.71–7.54 (m, 5 H), 7.45–7.43 (m,
1 H), 7.28–7.15 (m, 4 H), 7.06–7.01 (m, 2 H) ppm. 13C NMR
(CDCl3, 100 MHz): δ = 198.1, 156.7, 148.9, 139.5, 137.9, 136.2,
132.2, 130.1, 129.4, 129.0, 128.7, 128.4, 127.9, 122.6, 121.8 ppm.
MS (EI): m/z (%) = 259, 230, 182, 127, 77.
[2-(Pyridin-2-yl)phenyl](p-tolyl)methanone (5b):[12] CAS number
1173294-90-0. White solid, yield 75 %. 1H NMR (CDCl3,
400 MHz): δ = 8.39 (d, J = 4.30 Hz, 1 H), 7.77 (d, J = 7.64 Hz, 1
H), 7.62–7.47 (m, 7 H), 7.09–7.01 (m, 3 H), 2.32 (s, 3 H) ppm. 13C
NMR (CDCl3, 100 MHz): δ = 197.9, 156.9, 149.0, 143.1, 139.6,
139.5, 136.2, 135.2, 130.0, 129.7, 128.9, 128.8, 128.7, 128.3, 122.8,
121.8, 21.5 ppm. MS (EI): m/z (%) = 273, 244, 182, 127, 91.
number 1271322-37-2. White solid, yield 78%. H NMR (CDCl3,
400 MHz): δ = 8.36 (d, J = 4.12 Hz, 1 H), 7.77 (d, J = 7.68 Hz, 1
H), 7.70–7.48 (m, 8 H), 7.40–7.36 (m, 1 H), 7.01 (t, J = 6.0 Hz, 1
H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 196.1, 157.2, 149.0,
140.5, 139.3, 138.1, 136.1, 132.9, 131.5, 131.1, 130.5, 130.2, 129.3,
128.5, 125.9, 122.8, 121.8 ppm. MS (EI): m/z (%) = 293, 258, 230,
182, 127.
[2-(Pyridin-2-yl)phenyl](m-tolyl)methanone (5i):[12] CAS number
1271322-40-7. White solid, yield 67 %. 1H NMR (CDCl3,
400 MHz): δ = 8.38 (d, J = 4.36 Hz, 1 H), 7.76 (d, J = 7.64 Hz, 1
H), 7.62–7.46 (m, 7 H), 7.22–7.13 (m, 2 H), 7.04–7.01 (m, 1 H),
2.28 (s, 3 H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 198.3, 156.9,
149.0, 139.7, 139.6, 137.73, 137.70, 136.2, 133.1, 130.1,129.9, 129.1,
128.8, 128.3, 127.9, 126.9, 122.7, 121.9, 21.1 ppm. MS (EI): m/z
(%) = 273, 244, 182, 127, 91.
(E)-Phenyl[2-(phenyldiazenyl)phenyl]methanone (7a):[10c] CAS
number 54184-68-8. Red solid, yield 73 %. 1H NMR (CDCl3,
400 MHz): δ = 7.95 (d, J = 7.56 Hz, 1 H), 7.77 (d, J = 7.12 Hz, 2
H), 7.66–7.60 (m, 3 H), 7.48–7.33 (m, 8 H) ppm. 13C NMR
(CDCl3, 100 MHz): δ = 197.1, 152.1, 150.4, 138.5, 136.9, 132.7,
131.3, 130.8, 130.7, 129.4, 128.9, 128.8, 128.3, 122.9, 120.0 ppm.
MS (EI): m/z (%) = 286, 270, 152, 105, 77.
(4-Methoxyphenyl)[2-(pyridin-2-yl)phenyl]methanone (5c):[12] CAS
1
number 1236046-45-9. White solid, yield 72%. H NMR (CDCl3,
400 MHz): δ = 8.42 (d, J = 4.28 Hz, 1 H), 7.77 (d, J = 7.68 Hz, 1
H), 7.68 (d, J = 8.64 Hz, 2 H), 7.61–7.45 (m, 5 H), 7.06–7.03 (m,
1 H), 6.76 (d, J = 8.72 Hz, 2 H), 3.79 (s, 3 H) ppm. 13C NMR
(CDCl3, 100 MHz): δ = 196.9, 162.9, 156.9, 149.1, 139.6, 139.4,
136.1, 131.8, 130.7, 130.0, 128.9, 128.7, 128.3, 122.9, 121.8, 113.3,
55.3 ppm. MS (EI): m/z (%) = 289, 260, 182, 127, 77.
(E)-[2-(Phenyldiazenyl)phenyl](p-tolyl)methanone (7b):[10c] Red so-
lid, yield 61 %. 1H NMR (CDCl3, 400 MHz): δ = 7.94 (d, J =
7.08 Hz, 1 H), 7.69–7.56 (m, 5 H), 7.47 (s, 2 H), 7.36 (s, 3 H),
7.18 (d, J = 6.60 Hz, 2 H), 2.36 (s, 3 H) ppm. 13C NMR (CDCl3,
100 MHz): δ = 196.7, 152.1, 150.3, 143.6, 137.4, 135.9, 131.2, 130.8,
130.5, 129.6, 129.1, 128.9, 128.6, 122.9, 119.7, 21.61 ppm. MS (EI):
m/z (%) = 300, 284, 165, 152, 77.
(4-Fluorophenyl)[2-(pyridin-2-yl)phenyl]methanone (5d):[12] CAS
1
number 1236046-46-0. White solid, yield 80%. H NMR (CDCl3,
(E)-(4-Methoxyphenyl)[2-(phenyldiazenyl)phenyl]methanone (7c):[10c]
400 MHz): δ = 8.36 (d, J = 4.12 Hz, 1 H), 7.78–7.51 (m, 8 H), 7.07–
7.00 (m, 1 H), 6.93 (t, J = 8.52 Hz, 2 H) ppm. 13C NMR (CDCl3,
100 MHz): δ = 196.6, 165.2 (d, J = 252.5 Hz), 156.5, 148.9, 139.3,
139.1, 136.4, 134.2 (d, J = 2.62 Hz), 131.9 (d, J = 9.23 Hz), 130.2,
128.9, 128.7, 128.5, 122.6, 122.0, 115.1 (d, J = 21.76 Hz) ppm. MS
(EI): m/z (%) = 277, 248, 182, 127, 95.
1
Red solid, yield 62%. H NMR (CDCl3, 400 MHz): δ = 7.93 (d, J
= 7.04 Hz, 1 H), 7.77 (d, J = 7.52 Hz, 2 H), 7.63–7.51 (m, 5 H),
7.37 (s, 3 H), 6.86 (d, J = 7.60 Hz, 2 H), 3.82 (s, 3 H) ppm. 13C
NMR (CDCl3, 100 MHz): δ = 195.7, 163.4, 152.2, 150.1, 137.8,
131.9, 131.4, 131.3, 130.8, 130.4, 128.9, 128.5, 123.0, 119.3, 113.6,
55.4 ppm. MS (EI): m/z (%) = 316, 300, 168, 135, 77.
(4-Chlorophenyl)[2-(pyridin-2-yl)phenyl]methanone (5e):[12] CAS
(E)-(4-Fluorophenyl)[2-(phenyldiazenyl)phenyl]methanone (7d):[10c]
CAS number 1421276-20-1. Red solid, yield 71 %. 1H NMR
(CDCl3, 400 MHz): δ = 7.96 (d, J = 7.20 Hz, 1 H), 7.80 (s, 2 H),
7.67–7.57 (m, 3 H), 7.47 (s, 2 H) 7.37 (s, 3 H), 7.04 (d, J = 7.4 Hz,
2 H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 195.5, 166.7, 164.2,
151.9, 150.3, 136.5, 134.8, 131.9 (d, J = 9.25 Hz), 131.5, 130.9 (d,
J = 3.13 Hz), 129.4, 128.9, 128.6, 122.8, 120.2, 115.4 (d, J =
21.87 Hz) ppm. MS (EI): m/z (%) = 304, 199, 170, 95, 77.
1
number 1173294-91-1. White solid, yield 73%. H NMR (CDCl3,
400 MHz): δ = 8.34 (d, J = 4.2 Hz, 1 H), 7.77 (d, J = 7.68 Hz, 1
H), 7.63–7.52 (m, 7 H), 7.23 (d, J = 8.4 Hz, 2 H), 7.04 (t, J =
5.92 Hz, 1 H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 196.7, 156.4,
148.8, 139.3, 139.0, 138.4, 136.4, 130.6, 130.2, 128.9, 128.58,
128.55, 128.54, 128.2, 122.4, 122.0 ppm. MS (EI): m/z (%) = 293,
264, 182, 127, 111.
(4-Bromophenyl)[2-(pyridin-2-yl)phenyl]methanone (5f):[12] CAS
number 1173294-92-2. Pale yellow solid, yield 70 %. 1H NMR
(CDCl3, 400 MHz): δ = 8.34 (d, J = 4.24 Hz, 1 H), 7.77 (d, J =
7.72 Hz, 1 H), 7.62–7.52 (m, 7 H), 7.40 (d, J = 8.4 Hz, 2 H), 7.05
(t, J = 5.88 Hz, 1 H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 196.9,
156.3, 148.8, 139.3, 138.9, 136.8, 136.4, 131.2, 130.7, 130.3, 128.9,
128.58, 128.56, 127.2, 122.4, 122.1 ppm. MS (EI): m/z (%) = 337,
308, 182, 127, 76.
(E)-(4-Chlorophenyl)[2-(phenyldiazenyl)phenyl]methanone (7e):[10c]
CAS number 1421276-19-8. Red solid, yield 73 %. 1H NMR
(CDCl3, 400 MHz): δ = 7.97 (d, J = 7.20 Hz, 1 H), 7.72–7.57 (m,
5 H), 7.46–7.34 (m, 7 H) ppm. 13C NMR (CDCl3, 100 MHz): δ =
195.8, 151.9, 150.3, 139.1, 136.9, 136.2, 131.5, 131.0, 130.9, 130.7,
129.0, 128.7, 128.6, 122.9, 120.5 ppm. MS (EI): m/z (%) = 320, 152,
139, 105, 77.
Eur. J. Org. Chem. 2015, 7919–7925
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
7923

F. Xiao, S. Chen, H. Huang, G.-J. Deng
FULL PAPER
(E)-(4-Bromophenyl)[2-(phenyldiazenyl)phenyl]methanone (7f):[10c]
CAS number 1421276-18-7. Red solid, yield 75 %. 1H NMR
(CDCl3, 400 MHz): δ = 7.97 (d, J = 7.18 Hz, 1 H), 7.67–7.38 (m,
12 H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 195.9, 151.9, 150.3,
137.3, 136.1, 131.6, 131.5, 131.0, 130.9, 130.8, 129.90, 128.7, 127.8,
122.8, 120.5 ppm. MS (EI): m/z (%) = 364, 180, 152, 105, 77.
3.54 (s, 3 H), 2.80 (t, J = 5.92 Hz, 2 H), 2.57 (t, J = 6.68 Hz, 2 H),
1.89–1.82 (m, 2 H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 197.7,
151.7, 140.5, 138.7, 138.3, 132.0, 129.5, 128.9, 128.4, 128.1, 126.3,
61.5, 30.3, 21.1 ppm. MS (EI): m/z (%) = 279, 248, 202, 115, 77.
[5-Methyl-2-(pyridin-2-yl)phenyl](phenyl)methanone (8g):[12] CAS
number 198478-62-5. White solid, yield 67%. 1H NMR (CDCl3,
400 MHz): δ = 8.34 (d, J = 4.36 Hz, 1 H), 7.71–7.65 (m, 3 H), 7.54–
7.23 (m, 7 H), 7.01–6.95 (m, 1 H), 2.45 (s, 3 H) ppm. 13C NMR
(CDCl3, 100 MHz): δ = 198.4, 156.6, 148.9, 139.4, 138.6, 137.9,
136.8, 136.1, 132.2, 130.8, 129.6, 129.3, 128.5, 127.9, 122.4, 121.6,
21.1 ppm. MS (EI): m/z (%) = 273, 244, 196, 167, 77.
(E)-(2-Chlorophenyl)[2-(phenyldiazenyl)phenyl]methanone (7g):[10c]
CAS number 1421276-28-9. Red solid, yield 53 %. 1H NMR
(CDCl3, 400 MHz): δ = 7.82 (d, J = 7.40 Hz, 1 H), 7.73 (d, J =
7.80 Hz, 1 H), 7.67–7.53 (m, 3 H), 7.41–7.26 (m, 8 H) ppm. 13C
NMR (CDCl3, 100 MHz): δ = 195.7, 152.3, 151.1, 139.9, 137.1,
132.3, 132.2, 131.7, 131.4, 130.8, 130.7, 130.6, 130.0, 128.8, 126.6,
123.2, 117.7 ppm. MS (EI): m/z (%) = 320, 285, 152, 105, 77.
[5-Methoxy-2-(pyridin-2-yl)phenyl](phenyl)methanone (8h):[12] CAS
1
number 1173294-82-0. White solid, yield 52%. H NMR (CDCl3,
(E)-[2-(Phenyldiazenyl)phenyl](m-tolyl)methanone (7h):[10c] CAS
number 1421276-26-7. Red solid, yield 68%. 1H NMR (CDCl3,
400 MHz): δ = 7.94 (d, J = 7.48 Hz, 1 H), 7.66–7.45 (m, 7 H), 7.36–
7.29 (m, 4 H), 2.33 (s, 3 H) ppm. 13C NMR (CDCl3, 100 MHz): δ
= 197.2, 152.1, 150.4, 138.5, 138.1, 137.2, 133.5, 131.2, 130.7, 130.6,
129.7, 128.8, 128.7, 128.2, 126.9, 122.9, 119.8, 21.2 ppm. MS (EI):
m/z (%) = 300, 284, 165, 152, 77.
400 MHz): δ = 8.31 (d, J = 4.28 Hz, 1 H), 7.73–7.68 (m, 3 H), 7.52–
7.36 (m, 3 H), 7.26 (d, J = 5.0 Hz, 2 H), 7.14–7.11 (m, 1 H), 7.05
(d, J = 2.20 Hz, 1 H), 6.97–6.92 (m, 1 H), 3.88 (s, 3 H) ppm. 13C
NMR (CDCl3, 100 MHz): δ = 197.9, 159.8, 156.3, 148.8, 140.8,
137.7, 136.2, 132.3, 132.0, 129.9, 129.3, 128.0, 122.0, 121.3, 116.1,
114.0, 55.53 ppm. MS (EI): m/z (%) = 289, 260, 212, 169, 77.
[5-Chloro-2-(pyridin-2-yl)phenyl](phenyl)methanone (8i):[12] CAS
1
1-(2-Benzoyl-4-methylphenyl)ethanone O-Methyl Oxime (8a):[5b]
number 1236046-60-8. White solid, yield 71%. H NMR (CDCl3,
1
400 MHz): δ = 8.34 (d, J = 4.40 Hz, 1 H), 7.73–7.66 (m, 3 H), 7.59–
7.54 (m, 2 H), 7.51–7.39 (m, 3 H), 7.29–7.26 (m, 2 H), 7.04–7.01
(m, 1 H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 196.6, 155.5,
149.1, 140.9, 137.9, 137.3, 136.4, 134.8, 132.6, 130.1, 129.9, 129.3,
128.9, 128.1, 122.4, 122.1 ppm. MS (EI): m/z (%) = 293, 264, 216,
153, 77.
White solid, yield 65%. H NMR (CDCl3, 400 MHz): δ = 7.70 (d,
J = 7.32 Hz, 1 H), 7.53–7.49 (m, 1 H), 7.41–7.28 (m, 5 H), 3.65 (s,
3 H), 2.41 (s, 3 H), 2.01 (s, 3 H) ppm. 13C NMR (CDCl3,
100 MHz): δ = 197.8, 153.7, 138.8, 138.7, 138.3, 133.5, 132.4, 130.7,
129.5, 129.2, 128.1, 127.5, 61.5, 21.1, 14.2 ppm. MS (EI): m/z (%)
= 267, 236, 222, 105, 77.
(Benzo[h]quinolin-10-yl)(phenyl)methanone (8j):[12] CAS number
198478-50-1. White solid, yield 85%. 1H NMR (CDCl3, 400 MHz):
δ = 8.51 (d, J = 3.0 Hz, 1 H), 8.12–8.05 (m, 2 H), 7.91 (d, J =
8.8 Hz, 1 H), 7.81–7.73 (m, 4 H), 7.63 (d, J = 7.0 Hz, 1 H), 7.43–
7.28 (m, 4 H) ppm. 13C NMR (CDCl3, 100 MHz): δ = 198.5, 147.0,
144.5, 139.2, 138.8, 135.2, 133.7, 131.6, 129.1, 128.9, 128.6, 128.0,
127.7, 127.6, 126.9, 126.3, 126.1, 121.6 ppm. MS (EI): m/z (%) =
283, 254, 206, 178, 127, 77.
{5-Methoxy-2-[1-(methoxyimino)ethyl]phenyl}(phenyl)methanone
(8b):[18] CAS number 1401733-63-8. Pale yellow solid, yield 68%.
1H NMR (CDCl3, 400 MHz): δ = 7.71 (d, J = 7.48 Hz, 2 H), 7.53–
7.50 (m, 1 H), 7.44–7.38 (m, 3 H), 7.06–6.98 (m, 2 H), 3.85 (s, 3
H), 3.64 (s, 3 H), 1.99 (s, 3 H) ppm. 13C NMR (CDCl3, 100 MHz):
δ = 197.2, 159.8, 153.3, 140.2, 138.1, 132.5, 129.2, 128.9, 128.2,
127.5, 115.9, 114.0, 61.5, 55.5, 14.1 ppm. MS (EI): m/z (%) = 283,
252, 238, 105, 77.
(E)-[5-Methyl-2-(p-tolyldiazenyl)phenyl](phenyl)methanone
(8k):[10c] CAS number 1421276-37-0. Red solid, yield 51%. 1H
NMR (CDCl3, 400 MHz): δ = 7.85 (d, J = 8.16 Hz, 1 H), 7.76 (d,
J = 7.32 Hz, 2 H), 7.48–7.42 (m, 2 H), 7.38–7.28 (m, 5 H), 7.10 (d,
J = 8.04 Hz, 2 H), 2.48 (s, 3 H), 2.33 (s, 3 H) ppm. 13C NMR
(CDCl3, 100 MHz): δ = 197.5, 150.2, 148.5, 141.7, 141.4, 138.6,
136.7, 132.6, 131.5, 129.5, 129.3, 129.1, 128.2, 122.7, 120.2,
21.4 ppm. MS (EI): m/z (%) = 314, 298, 165, 152, 91.
{5-Chloro-2-[1-(methoxyimino)ethyl]phenyl}(phenyl)methanone
(8c):[18] CAS number 1417412-29-3. Pale yellow solid, yield 78%.
1H NMR (CDCl3, 400 MHz): δ = 7.70 (d, J = 7.36 Hz, 2 H), 7.56–
7.49 (m, 2 H), 7.45–7.40 (m, 4 H), 3.65 (s, 3 H), 2.01 (s, 3 H) ppm.
13C NMR (CDCl3, 100 MHz): δ = 195.9, 152.7, 140.3, 137.5, 134.8,
134.6, 132.8, 130.1, 129.2, 128.9, 128.8, 128.3, 61.7, 14.0 ppm.
MS (EI): m/z (%) = 287, 256, 242, 152, 77.
{2-[1-(Methoxyimino)propyl]phenyl}(phenyl)methanone (8d): White
solid, yield 67%. 1H NMR (CDCl3, 400 MHz): δ = 7.72 (d, J =
7.16 Hz, 2 H), 7.55–7.46 (m, 6 H), 7.41–7.37 (m, 2 H), 3.66 (s, 3
H), 2.57 (q, J = 7.61 Hz, 2 H), 0.99 (t, J = 7.60 Hz, 3 H) ppm. 13C
NMR (CDCl3, 100 MHz): δ = 197.6, 158.5, 139.5, 138.2, 135.3,
132.4, 130.0, 129.5, 129.0, 128.4, 128.1, 127.6, 61.5, 21.3, 10.4 ppm.
MS (EI): m/z (%) = 267, 236, 207, 105, 77.
Acknowledgments
This work was supported by the National Natural Science Founda-
tion of China (NSFC) (grant numbers 21172185, 21372187,
21502160, 21572194), the Hunan Provincial Education Department
(project 15C1311, supported by the Scientific Research Fund), and
the China Postdoctoral Science Foundation (project number
2015M572257).
2-Benzoylbenzaldehyde O-Methyl Oxime (8e):[18] CAS number
1417412-48-6. Pale yellow solid, yield 53 %. 1H NMR (CDCl3,
400 MHz): δ = 8.15 (s, 1 H), 7.90 (d, J = 7.72 Hz, 1 H), 7.78 (d, J
= 7.44 Hz, 2 H), 7.61–7.41 (m, 6 H), 3.85 (s, 3 H) ppm. 13C NMR
(CDCl3, 100 MHz): δ = 197.0, 146.3, 138.3, 137.5, 133.2, 130.5,
130.1, 129.0, 128.9, 128.4, 127.2, 62.0, 26.2 ppm. MS (EI): m/z (%)
= 239, 208, 130, 105, 77.
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Received: September 11, 2015
Published Online: November 13, 2015
Eur. J. Org. Chem. 2015, 7919–7925
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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