Palladium catalyzed decarboxylative acylation of arylboronic acid with ethyl cyanoacetate as a new acylating agent: Synthesis of alkyl aryl ketones

Article abstract of DOI:10.1039/c5nj01597a

Palladium catalyzed acylation of arylboronic acid containing various functional groups was performed efficiently by ethyl cyanoacetate/substituted ethyl cyanoacetate as the acylating agent in aqueous triflic acid medium. The alkyl aryl ketones were obtained in good to excellent yields, first by addition of arylboronic acid to the nitrile group of ethyl cyanoacetate and their derivatives, followed by in situ decarboxylation of the resulting β-ketoester.

Full text of DOI:10.1039/c5nj01597a

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Palladium catalyzed decarboxylative acylation of arylboronic acid
with ethyl cyanoacetate as a new acylating agent: synthesis of
alkyl aryl ketones
Received 00th January 20xx,
Accepted 00th January 20xx
Md Yousuf,a Tuluma Das,b and Susanta Adhikari*a
DOI: 10.1039/x0xx00000x
Palladium catalyzed acylation of arylboronic acid containing various functional groups was performed efficiently by ethyl
cyanoacetate/substituted ethyl cyanoacetate as acylating agent in aqueous triflic acid medium. The alkyl aryl ketones were
obtained in good to excellent yields first by addition of arylboronic acid to nitrile group of ethyl cyanoacetate and their
derivatives, followed by in situ decarboxylation of the resulting ß-ketoester.
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in the presence of palladium catalysts leading to α-arylation
products.13 Thus, the addition reaction to aliphatic nitriles is
generally morechallenging than that of aromatic nitriles. On
Introduction
Alkyl aryl ketones are common and important intermediates in
the agrochemical, pharmaceutical, fragrance, and dye
industries.1 Alkyl aryl ketones are conventionally synthesized
by Friedel-Crafts acylation, which involves activation of
electrophile with hazardous reagents and further limits to
electron rich arenes.2 Discovery of catalytic transformation,
especially the transition metal catalyzed C–C bond formation
provides useful alternative to such stoichiometric reactions for
the commercial synthesis of important intermediates.
Transition metal catalyzed addition of arylboronic acid to
nitriles emerged as an improvement over the conventional
methods of syntheses of aryl ketones because of wider
functional group compatibility and ease of handling. Recently,
a significant amount of research has been devoted to addition
the other hand ethyl cyanoacetate is an inexpensive, nontoxic
and easy to handle organic reagent for acylation of arylboronic
acid. Functionalization is also possible due to the presence of
active methylene hydrogen in ethyl cyanoacetate by most
simple technique14 which opens up broad substrate scope for
this method to have wide applications.
In most of the cases of acylation of arylboronic acid9,10,11
reported earlier, phosphine based ligands were employed.
Our initial effort seeking to explore pyrazole tethered donors
as effective ligands15 in metal catalysed reactions led us to
identify a non-phosphorus based pyrazole tethered pyridine
ligand L. This ligand can coordinate with palladium effectively
and thereby catalyze an addition reaction of arylboronic acid
to aryl aldehydes16a and nitriles16b in aqueous triflic acid
medium. In our previous work16b we have observed that
aliphatic nitriles in spite of having lower electrophilicity,
showed excellent results and when ethyl cyanoacetate was
used as nitrile coupling partner with phenylboronic acid,
acetophenone was obtained as acylation product of
phenylboronic acid via in situ decarboxylation of the initially
formed ß-keto ester as the medium was acidic. In reference to
that we wanted to explore whether ethyl cyanoacetate can be
used as acylating agent for arylboronic acid in general. Here in,
we describe for the first time decarboxylative acylation of
arylboronic acid using ethyl cyanoacetate/substituted ethyl
of
arylboronic
acids
to
nitriles
catalyzed
by
rhodium,3palladium,4 and nickel.5 However, in most cases, the
substrate scope is limited to aromatic nitriles and activated
nitriles.3b,3c Alternative routes for transition metal catalyzed
synthesis of unsymmetrical ketones are hydroacylation from
reaction of aldehydes and olefins,6 acylation of aryl halides,7
and carbonylative cross-coupling reaction.8 For the synthesis
of alkyl aryl ketones from arylboronic acids the use of
anhydrides,9 acid chlorides,10 and esters11 as acylating source,
were most common unlike that of aliphatic nitriles.12 This is
because electrophilic activation of aliphatic nitrile is not
sufficient enough to perform nucleophilic addition reactions
and also aliphatic nitriles have tendency to get deprotonated
O
O
Pd-Cat./aq. Acid
-CO2
NC
R1
R2
Ar B(OH)2
OEt
Ar
R2
R1
a.Department of Chemistry, University of Calcutta.92, A.P.C. Road, Kolkata 700 009
(India). E-mail: adhikarisusanta@yahoo.com
Scheme 1.Alkyl aryl ketone synthesis by decarboxylative acylation of arylboronic
acid by ethyl cyanoacetate/substituted ethyl cyanoacetate
b.Department of Organic Chemistry, Indian Association for the Cultivation of
Science, Jadavpur, Kolkata 700032 (India).
.
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cyanoacetate as an acylating agent in presence of non- Table 1. Scope of arylboronic acid substrates in Pd-catalyzed
phosphine based pyrazole-pyridine ligand. This convenient acylationa
synthesis of alkyl aryl ketones appears to involve both the
O
O
Pd(OAc)2, L
addition of aryl group of arylboronic acid to nitriles and
decarboxylation of the resultant β-ketoester in the same
reaction system (Scheme 1).
ArB(OH)2
NC
H2O/TfOH(3:1)
OEt
Ar
CH3
2a-j
1a-j
L=
N
N
N
Yieldb
(%)
Time
(h)
Entry Bronic Acid
Product
O
Results and Discussion
Initially, with a view to generalize the acylation reaction of
appropriate commercially available arylboronic acids by ethyl
cyanoacetate, the optimized reaction condition mentioned in
our recent report16b was followed. Subsequently all the
reactions were carried out by
procedure: ethyl cyanoacetate (0.5 mmol), arylboronic acid
(0.6 mmol), Pd(OAc)2, (4 mol%) and ligand (4 mol%) in water-
B(OH)2
1a
89
98
5
5
CH3
CH3
1
2a
O
a general experimental
B(OH)2
2
L
trifllic acid mixture (3:1) were heated at 60 °C for 5h and
progress of the reaction was monitored by TLC. Standard work
up with ethyl acetate followed by purification on silica gel
column chromatography afforded the pure products. A large
number of electronically and structurally diverse arylboronic
acids were explored under this reaction condition and in most
of the cases acylated products 2a-u were obtained in good to
excellent yields. Results are summarized in Table 1.
CH3
CH3
O
1b
2b
B(OH)2
CH3
3
5
5
72
2c
F
F
1c
O
B(OH)2
4
5
66
CH3
Arylboronic acids containing electron donating groups (1b
1j 1k and 1t; Table 1) provided excellent yields except 2-
hydroxy phenylboronic acid 1e and 2, 4-dicholoro
, 1e,
Br
,
Br
1d
1e
O
(
)
2d
B(OH)2
phenylboronic acid (1o) probably because of steric reason. For
these two substrates elevation of temperature enhance the
yield above 70%. Lack of reactivity in case of electron
31(80)c
8
CH3
OH
OH
O
withdrawing groups substituted phenylboronic acid (1g, 1i;
2e
Table 1) can be compensated by increasing the temperature.
This is perhaps due to lower nucleophilicity of the aryl group of
arylboronic acid which slows down the transmetalation step to
cationic Pd(II) complex (vide infra, Scheme 2).17 Sterically
B(OH)2
CH3
93
5
8
5
8
5
6
1f
2f
hindered arylboronic acids (1b, 1e, 1r, 1t, 1u; Table 1) also
CH3
CH3
afforded products in good to excellent yields. Despite heating
in a strongly acidic medium, it is remarkable to note that the
desired alkyl aryl ketones were obtained from -OH, -OMe,NO2,
O
B(OH)2
B(OH)2
B(OH)2
35(71)c
CH3
CH3
CH3
CH3
7
-X (Cl, Br, F) substituted phenylboronic acids in high yields (1c
,
,
1d 1e 1h 1i 1j 1k 1l 1m 1n, 1o and 1p respectively). This
2g
,
,
,
,
,
,
,
1g
CF3
offers a clear opportunity for these substrates to undergo
further transformation. Acetyl group can also be appended at
3-position of thiophene in very good yield when 3-
thiopheneboronic (1q) acid was used as starting material
(Entry 15, Table 1).
CF3
O
90
8
1h
2h
F
On the other hand, the superior control of the regioselectivity
i.e. addition to nitrile, rather than substitution at α-carbon of
ethyl cyanoacetate to obtain α-arylcyanoester which is the
common product when ethyl cyanoacetate reacts with aryl
halide in presence of Pd catalyst and ligand,13 was observed.
F
O
32(68)c
9
1i
For example, arylboronic acid 1c, 1d, 1h, 1l, 1m, 1n, 1o and 1p
2i
NO2
NO2
containing halide groups were tolerated in our reaction
condition giving excellent yields of the desired ketone without
any trace of α-arylcyanoester products.
O
B(OH)2
72
10
1j
OCH3
2j
Encouraged by these results, we thought of extending the
decarboxylative acylation strategy for substituted ethyl
cyanoacetate. For mono substituted small chain
ethylcyanoacetate derivative, desired acylation product were
obtained but when we switched to the disubstituted, cyclic
and long chain derivatives of ethylcyanoacetate, it resulted in
desired products along with non-decarboxylative products.
However, in case of hexadecyl derivative non-
OCH3
aReaction condition: ArB(OH)2 (1.2 mmol), Ethyl cyanoacetate (1 mmol), H2O/TfOH
(1.2 mL/0.4 mL), Pd(OAc)2 (4 mol %), L (4 mol %), under air, 60 °C. bIsolated yields.
c At 90 °C.
2 | J. Name., 2012, 00, 1-3
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phenylboronic acid following the condition mentioned in Table
1, acylation product was the only isolable product (entry 1,
Table 2). But under same condition ethyl 2-
cyanohexanoate(3c, Table 2) resulted in desired product along
with non-decarboxylative product (entry 2, Table 2) and even
at high temperature the formation of 1-phenylhexan-1-one i.e.
the desired acylation product was not favored also (entry
3,Table 2) making this optimization study specific for hindered
ethyl cyanoacetate derivatives. For optimization studies, ethyl
2-cyanohexanoate(3c, Table 2) and phenylboronic acid were
selected as reaction partners. First, we performed the
reaction in dioxane/water/TfOH in 3:3:2 ratio (entry 4, Table 2)
but it resulted in homocoupling of phenylboronic acid. Keeping
the water-TfOH ratio intact under table 1 condition, when
switched to stoichiometric amount of organic solvent, we
observed a facile decarboxylaion. In a solvent of high polarity
such as in DMSO, DMF, PEG and ethanol, the reaction resulted
in moderate yield but in nitromethane the catalytic reaction
did not proceed at all.
Table 1 Contd.
O
O
Pd(OAc)2, L
ArB(OH)2
NC
Ar
2k-u
CH3
OEt
H2O/TfOH(3:1)
1k-u
L=
N
N
N
Time
(h)
Yield
(%)
Bronic Acid
Entry
Product
O
B(OH)2
1k
11
H3CO
CH3
CH3
5
5
82
2k
H3CO
O
B(OH)2
12
81
1l
2l
F
F
O
B(OH)2
1m
CH3
CH3
13
14
5
5
Table 2. Optimisation studiesa
73
2m
O
Cl
Cl
B(OH)2
1n
86
2n
Br
Br
O
B(OH)2
34(70)c
CH3
15
8
Cl
Cl
Cl
Cl
O
1o
2o
B(OH)2
1p
CH3
CH3
16
17
91
80
98
5
5
5
Cl
2p
Cl
Cl
O
Cl
B(OH)2
1q
S
2q
S
B(OH)2
H3C
O
18
19
1r
2r
O
B(OH)2
5
5
91
85
CH3
CH3
2s
1s
O
20
21
B(OH)2
1t
2t
H3C
H3C
B(OH)2
1u
O
5
98
CH3
2u
aReaction condition : Phenylboronic acid (1.2 mmol), ethyl 2-cyanohexanoate (1
mmol), Pd(OAC)2 (4 mol%), L (4 mol%), organic solvent (1 eq.), under air, 60 °C.
bProduct distribution by isolated yield. cWith ethyl cyanoacetate. dAt 90 °C
eDioxane/H2O/TfOH (3:3:2), fNo ligand used, gNo Pd(OAc)2.
aReaction condition: ArB(OH)2 (1.2 mmol), ethyl cyanoacetate (1 mmol), H2O/TfOH
(1.2 mL/0.4 mL), Pd(OAc)2 (4 mol %), L (4 mol %), under air, 60 °C. bIsolated yields.
cAt 90 °C.
Among other solvents such as toluene, tetrahydrofuran (THF),
dimethoxyethane (DME), dioxane and dichloroethane (DCE)
respectively, DME is superior. Also, the reaction did not
proceed in the absence of the ligand; and the reaction mixture
immediatelyturned black indicating precipitation of palladium
decarboxylativeproduct was isolated exclusively. Therefore, it
is of particular interest to increase the substrate scope. In a
quest to facilitate the decarboxylation for these particular
substrates, we freshly screened the reaction of phenylboronic
acid and ethyl 2-cyanohexanoate(3c, Table 2) with different
organic solventsin combination with water and triflic acid.
Initially, when ethyl cyanoacetate was reacted with
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Table3. Scope of ethyl cyanoacetate in Pd-catalyzed acylation of phenylboronicacida
O
O
Pd(OAc)2, L
N
N
N
NC
PhB(OH)2
L=
Time/h
5
OEt
3a-j
Ar
CH3
4a-j
H2O/TfOH(3:1)
DME (1 eq)
R
1a
Yieldb
95c
Entry
1
Ethylcyanoacetate Derivative (R)
Product
O
O
CH3
H3C
OEt
4a
3a
CN
O
O
99c
2
5
CH3
H3C
OEt
CN 3b
4b
O
O
3
4
5
12
12
97
90
CH3
Br
H3C
Br
OEt
3c
4c
CN
O
O
OEt
4d
CN
3d
O
O
C8H17
C8H17
12
12
94
70d
75
OEt
3e
4e
CN
O
O
C16H33
C16H33
OEt
3f
6
7
4f
CN
H3C
H3C
O
O
CH3
CH3
12
OEt
3g
4g
CN
O
O
8
OEt
12
5
70
CN
O
3h
4h
O
78c
91c
OEt
3i
9
4i
CN
O
OMe
MeO
O
CH3
10e
5
4j
H3C
OEt
3b
CN
aReaction condition: ArB(OH)2 (1.2 mmol), ethyl cyanoacetate derivative (1 mmol), H2O/TfOH (1.2 mL/0.4 mL), DME (1 eq.), Pd(OAc)2 (4 mol %), L (4 mol %), under air,
60
C. bIsolated yield. cReaction was performed under condition of Table 1. dAt 90 C, e1-naphthylboronic acid was used.
°
°
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black (entry 15, Table 2).The results of the reaction
ofarylboronic acidand substituted ethyl cyanoacetates are
presented in Table 3(containing both the conditions of Table 1
and modified optimization condition). Mono substituted small
Scheme 3.
Ligand
H2O/TfOH(3:1)
O
O
O
Pd(OAc)2
Ligand
No
chain alkyl (3a
3)of ethyl cyanoacetate afforded almost quantitative yields
under optimized reaction condition as described before in
Table 1. The bromo alkyl substituted ethyl cyanoacetate (3d
,
3b; Table 3) and benzyl derivative (3i, Table
Ph
C5H11
Ph
OEt
H2O
DME (1 eq)
Reaction
DME (1 eq)
C4H9
°
60 C
4c
60 °C
,
No TfOH
No Pd(OAc)2
Table 3) remained intact under this condition, thus, offering
the scope forfurther transformation. The potential of present
strategy was further extended to cyclic derivative (3h, Table 3)
for the synthesis of cyclopentyl(phenyl)methanone
(4h)
Conclusions
ketone. However, the addition reaction of ethyl 2-
cyanooctadecanoate and phenyboronic acid required heating
to 90 °C, and 1-phenyloctadecan-1-one (4f, Table 3), was
isolated after 12h in 70% yield.
In conclusion, the protocol described here disclosed a new
variant of acylating agent for acylation of arylboronic acid by
an operationally simple, effective yet mild reaction condition
thus giving a new avenue for the synthesis of alkyl aryl ketone.
Designing of alkyl aryl ketone was enriched by the use of both
differently functionalized arylboronic acid and various
derivatives of ethylcyanoacetate. Also the method offers
several advantages in terms of reaction time, temperature,
yield, and convenience. These combined features render the
new reaction protocol useful for application in agrochemical
and pharmaceutical industries.
From our earlier observation and on the basis of suggestions
made in earlier report,16b we can speculate a plausible
mechanism of this transformation as shown in Scheme 2. First,
electrophilic transmetalation of arylboronic acid occurs by
cationic Pd(II) species (
17
)
B
to generate C. Then nitrile group
coordinates to the vacant coordination site of Pd giving
intermediate . Selective intramolecular migration of the aryl
group from Pd centre to the activated carbon of the nitrile
would result in the new C-C bond formation to afford
intermediate Finally protonolysis of affords and
regenerates the [Pd] catalyst. Once is generated, undergoes
D
E.
E
F
Experimental Section
F
General
hydrolysis followed by decarboxylation to give the desired
alkyl aryl ketone (Scheme 2).
Chemicals and solvents were purchased from commercial
suppliers and used as received. H and 13C NMR spectra were
1
Scheme 2. Proposed mechanism
recorded on a BrukerAvance III HD (300 MHz) or Avance III HD
(400 MHz) or Avance III 500 (500 MHz) spectrometer. Chemical
shifts were reported in parts per million (ppm), and the
residual solvent peak was used as an internal reference:
proton (chloroform δ 7.26), carbon (chloroform δ 77.16) or
tetramethylsilane (TMS δ 0.00) was used as a reference.
Multiplicity was indicated as follows: s (singlet), d (doublet), t
(triplet), q (quartet), m (multiplet), dd (doublet of doublet), br
s (broad singlet). Coupling constants were reported in Hertz
(Hz). High resolution mass spectra were obtained on a
Micromass/Q-Toff. microTM spectrometer. For thin layer
chromatography (TLC), Merck precoated TLC plates (Merck 60
F254) were used, and compounds were visualized with a UV
light at 254 nm. Further visualization was achieved by staining
with iodine. Flash chromatography separations were
performed on SRL 230-400 mesh silica gel.
L
L
OAc
OAc
L
L
OTf
OTf
L
L
-OTf
TfOH
Pd OTf
Pd
Pd
A
B
ArB(OH)2
H+
Ar
s
O
i
NH
L
s
y
l
TfOH
Pd
o
r
EtO
Ar
d
L
y
H
OTf
R
O
C
F
O
O
CN
EtO
HO
CO2
Ar
R
G
Sol
R
Ar
L
L
L
Pd
Pd
Decarboxylation
L
N
N
C
Ar
R
O
O
O
D
General procedure:To
mmol),ethyl cyanoacetate (1.0 mmol), Pd(OAc)2 (4 mol%) and
a mixture of arylboronic acid (1.2
L
R
OEt
Ar
R
E
OEt
H
(4 mol%), H2O (1.2 mL) and triflic acid (0.4 mL) were added and
stirred at 60 °C under air for desired time (TLC monitoring).
Then the reaction mixture was neutralized with saturated
NaHCO3 solution and extracted with ethylacetate. The
combined ethylacetate solution was washed with brine, dried
by Na2SO4 and concentrated. The residue was purified by flash
column chromatography on silica gel using petroleum
In order to confirm the role of TfOH/Pd(OAc)2 during
hydrolysis of β-ketoester, we have also performed the reaction
starting from separately isolated ethyl 2-benzoylhexanoate
following the condition of Table 3(Scheme 3).Result shows that
the presence of triflic acid is essential for decarboxylation of
the β-ketoester. Only when triflic acid was used, we obtained
the desired decarboxylation product (4c).
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ether/ethylacetate or petroleum ether/DCM as eluent to give
the desired product.
Hz), 124.2(d, JC,F = 2 Hz), 130.4(d, JC,F = 8 Hz), 139.4(JC,F = 5 Hz),
164.2(d, JC,F = 246 Hz), 196.8.
1-(3-Nitrophenyl)ethanone (2i):26White solid, 1HNMR(400
MHz, CDCl3): δ 2.69 (s, 3H), 7.69 (t, J = 7.8Hz, 1H), 8.29 (d, J =
8.8Hz, 1H), 8.43 (dd, J = 1Hz, J = 7.4Hz, 1H), 8.78 (t, J = 2Hz,
1H);13CNMR(100 MHz, CDCl3): δ 26.8, 123.4, 127.6, 130.0,
133.9, 138.5, 195.7.
Modified procedure for 4c, 4d, 4e, 4f, 4g, 4h of Table 3:To a
mixture of arylboronic acid (1.2 mmol),substituted ethyl
cyanoacetate (1.0 mmol), Pd(OAc)2 (4 mol%) and L (4 mol%),
H2O (1.2 mL), triflic acid (0.4 mL) and dimethoxyethane (1
mmol, 0.1 mL) were added and stirred at 60 °C under air for
12h. Then the reaction mixture was neutralized with saturated
NaHCO3 solution and extracted with ethyl acetate. The
combined ethyl acetate solution was washed with brine, dried
over Na2SO4 and concentrated. The residue was purified by
flash column chromatography on silica gel using petroleum
ether/Ethyl acetate or petroleum ether/DCM as eluent to give
the desired product.
1
1-(3-Methoxyphenyl)ethanone (2j):25Colorless oil, HNMR(400
MHz, CDCl3): δ 2.59 (s, 3H), 3.86 (s, 3H), 7.10-7.12 (m, 1H), 7.37
(t, J = 8Hz, 1H), 7.48 (t, J = 1.6Hz, 1H), 7.53 (d, J = 8Hz,
1H);13CNMR(100 MHz, CDCl3): δ 26.8, 55.6, 112.5, 119.7,
121.2, 129.7, 138.7, 160.0, 198.0.
1-(4-Methoxyphenyl)ethanone
(2k):12aColorless
oil,
1HNMR(400 MHz, CDCl3): δ 2.54 (s, 3H), 3.86 (s, 3H), 6.91-6.93
(m, 2H), 7.92-7.94 (m, 2H), 13CNMR(100 MHz, CDCl3): δ 26.4,
55.6, 113.8, 130.5, 130.7, 163.6, 196.9.
All the compounds describe here were known and further
identified by comparing their 1H and 13C spectroscopic data
with reported value and the spectra were included in
supporting information.
1-(4-Fluorophenyl)ethanone (2l):25Colorless oil, 1HNMR(500
MHz, CDCl3): δ 2.58 (s, 3H), 7.10-7.14 (m, 2H), 7.96-7.99 (m,
2H), 13CNMR(100 MHz, CDCl3): δ 26.6, 115.8 (d, JC,F = 22 Hz),
131.1 (d, JC,F = 9 Hz), 133.8 (d, JC,F = 3 Hz), 165.9 (d, JC,F = 253
Hz), 196.6.
1
Acetophenon (2a):16bColorless oil, H NMR(300 MHz, CDCl3): δ
2.61 (s, 3H), 7.44-7.49(m, 2H), 7.54-7.60 (m, 1H), 7.95-7.97 (m,
2H); 13CNMR(75 MHz, CDCl3): δ 26.7, 128.4,128.7, 133.2,
137.2, 198.2;
1-o-Tolylethanone (2b):12aColorless oil, 1HNMR(400 MHz,
CDCl3): δ 2.53 (s, 3H), 2.58 (s, 3H), 7.23-7.25 (m, 2H), 7.36-7.39
(m, 1H), 7.69 (d, J=7.6Hz, 1H);13CNMR(100 MHz, CDCl3): δ 21.7,
29.7, 125.8, 129.4, 131.6, 132.2, 137.9, 138.5, 201.9.
1-(2-Fluorophenyl)ethanone(2c):28Colorless oil, 1HNMR(500
MHz, CDCl3): δ2.64 (t, J = 5.25 Hz, 3H), 7.11-7.15 (m, 1H), 7.22
1
1-(4-Chlorophenyl)ethanone (2m):12aColorless oil, HNMR(500
MHz, CDCl3): δ 2.58 (s, 3H), 7.42-7.44 (m, 2H), 7.88-7.89 (m,
2H);13CNMR(100 MHz, CDCl3): δ 26.6, 129.0, 129.9, 135.6,
139.7, 196.9.
1
1-(4-Bromophenyl)ethanone (2n):32 White solid, H NMR (400
MHz, CDCl3): δ 2.57 (s, 3H), 7.59 (d, J =8.8 Hz, 2H), 7.80 (d, J =
8.4 Hz, 2H), 13C NMR (100 MHz, CDCl3): δ 26.6, 128.4, 129.91,
129.94, 132.0, 136.0, 197.1.
(t,J
= 7.5 Hz, 1H), 7.50-7.54 (m, 1H), 7.86-7.89 (m,
1H);13CNMR(125 MHz, CDCl3): δ31.6 (d, JC,F = 7.5 Hz), 116.8 (d,
1-(2,4-Dichlorophenyl)ethanone (2o):20Colorless sticky oil,
1HNMR(500 MHz, CDCl3): δ 2.64 (s, 3H), 7.32 (d, J = 8.5Hz, 1H),
7.45 (d, J = 1.5Hz, 1H), 7.54 (d, J = 8Hz, 1H);13CNMR(100 MHz,
CDCl3): δ 30.8, 127.5, 130.7, 130.8, 132.7, 137.4, 137.9, 199.0.
JC,F = 23.75 Hz), 124.5 (d, JC,F = 2.5 Hz), 130.7, 134.8 (d, JC,F
8.75 Hz), 162.4 (d, JC,F = 252.5 Hz), 196.1.
=
1-(2-Bromophenyl)ethanone (2d):32 Yellow oil, 1H NMR (300
MHz, CDCl3): δ 2.64 (s, 3H), 7.27-7.40 (m, 2H), 7.47 (dd, J = 1.6
Hz, J = 7.5 Hz, 1H), 7.62 (d, J = 7.8 Hz, 1H); 13C NMR (75 MHz,
CDCl3): δ 30.3, 118.9, 127.4, 128.9, 131.8, 133.8, 141.4, 201.4.
1-(3,4-Dichlorophenyl)ethanone
(2p):21White
solid,
1HNMR(400 MHz, CDCl3): δ 2.58 (s, 3H), 7.54 (d, J = 8.4Hz, 1H),
7.77 (dd, J = 2Hz, J = 8.4Hz 1H), 8.02 (d, J = 2Hz, 1H),
13CNMR(100 MHz, CDCl3): δ 26.7, 127.5, 130.5, 130.9, 133.5,
136.8, 137.9, 195.8.
1-(2-Hydroxyphenyl)ethanone(2e):29Pale
yellow
oil,
1HNMR(500 MHz, CDCl3): δ 2.64 (s, 3H), 6.9 (t, J=7.7Hz, 1H),
6.98 (d, J=8.5Hz, 1H), 7.48 (t, J=8Hz, 1H), 7.53 (d, J=8Hz, 1H),
12.25 (s, 1H), 13CNMR(100 MHz, CDCl3): δ 26.8, 118.6, 119.1,
119.9, 130.9, 136.2.6, 162.6, 204.7.
1
1-(Thiophen-3-yl)ethanone (2q):27Pale yellow oil, HNMR(500
MHz, CDCl3): δ 2.54 (s, 3H), 7.30-7.32 (m, 1H) 7.54 (d, J = 5Hz,
1H), 8.04 (d, J = 2Hz, 1H);13CNMR(100 MHz, CDCl3): δ 27.7,
126.5, 127.1, 132.4, 142.8, 192.4.
1-m-Tolylethanone (2f):12aColorless oil, 1HNMR(500 MHz,
CDCl3): δ 2.41 (s, 3H), 2.59 (s, 3H), 7.32-7.38 (m, 2H), 7.74-7.77
(m, 2H), 13CNMR(125 MHz, CDCl3): δ 21.5, 26.8, 125.7, 128.6,
128.9, 134.0, 137.4, 138.5, 198.5.
1-(Naphthalen-1-yl)ethanone
(2r):12aPale
yellow
oil,
1HNMR(500 MHz, CDCl3): δ 2.75 (s, 3H), 7.48-7.55 (m, 2H), 7.61
(t, J = 2.8Hz, 1H), 7.87 (d, J = 8Hz, 1H), 7.94 (d, J = 7Hz, 1H),
7.99 (d, J = 8.5Hz, 1H), 8.75 (d, J = 8.5Hz, 1H);13CNMR(125
MHz, CDCl3): δ 30.1, 124.5, 126.2, 126.6, 128.2, 128.5, 128.8,
130.3, 133.1, 134.1, 135.7, 202.0.
1-(3-(Trifluoromethyl)phenyl)ethanone(2g):20Colorless
oil,
1HNMR(500 MHz, CDCl3): δ 2.65 (s, 3H), 7.61 (t, J = 7.75 Hz,
2H), 7.82 (d, J= 8 Hz, 1H), 8.13 (d, J = 8 Hz, 1H), 8.20 (s,
1H);13CNMR(100 MHz, CDCl3): δ26.7, 122.5, 125.3 (t, JC,F = 4
Hz), 127.9, 129.4, 129.6 (t, JC,F = 3.5 Hz), 131.4 (q, JC,F = 35 Hz),
137.8, 196.7.
1-(Naphthalen-2-yl)ethanone
(2s):12aYellowish
solid,
1HNMR(400 MHz, CDCl3): δ 2.73 (s, 3H), 7.54-7.62 (m, 2H),
7.87-7.90 (m, 2H), 7.97 (d, J = 8Hz, 1H), 7.94 (d, J = 7Hz, 1H),
7.99 (d, J = 8.5Hz, 1H), 8.75 (d, J = 8.5Hz, 1H) 8.46 (s,
1H);13CNMR(125 MHz, CDCl3): δ 26.8, 124.0, 126.9, 127.9,
128.5, 128.6, 129.7, 130.3, 132.7, 134.7, 135.7, 198.2.
1-(3-Fluorophenyl)ethanone (2h):28Colorless oil, 1HNMR(400
MHz, CDCl3): δ 2.59 (s, 3H), 7.24-7.41 (m, 1H), 7.41-7.46 (m,
1H), 7.60-7.64(m, 1H), 7.72 (d, J = 7.6Hz, 1H), 13CNMR(100
MHz, CDCl3): δ 26.8, 115.1(d, JC,F = 22 Hz), 120.2(d, JC,F = 20
1-(4-Methylnaphthalen-1-yl)ethanone (2t):25Pale yellow sticky
oil,1HNMR(400 MHz, CDCl3): δ 2.73 (s, 3H), 2.74 (s, 3H), 7.34 (d,
J = 7.6Hz, 1H), 7.57-7.63 (m, 2H), 7.85 (d, J = 7.2Hz, 1H), 8.03-
6 | J. Name., 2012, 00, 1-3
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8.05 (m, 1H), 8.85 (d, J = 8Hz, 1H);13CNMR(125 MHz, CDCl3): δ 3-(4-Methoxyphenyl)-1-phenylpropan-1-one(4i):18
ARTICLE
white
20.2, 29.9, 124.4, 126.2, 126.6, 128.2, 128.5, 128.8, 130.3, solid,1HNMR(400 MHz, CDCl3): δ 3.02 (t, J=7.6Hz, 2H), 3.27 (t,
133.1, 134.1, 135.7, 202.0.
J=7.6Hz, 2H), 3.80 (s, 3H), 6.85 (d, J=8.4Hz, 2H), 7.17 (d,
(2u):19Pale J=8.4Hz, 2H), 7.45 (t, J=7.8Hz, 2H), 7.56 (t, J=7.2Hz, 1H), 7.96
1-(1,2-Dihydroacenaphthylen-5-yl)ethanone
yellow solid,1HNMR(500 MHz, CDCl3): δ 2.73 (s, 3H), 3.38- (d, J=8.4Hz, 2H); 13CNMR(100 MHz, CDCl3): δ 29.5, 40.9, 55.4,
3.43(q, 4H), 7.29 (d, J=8Hz, 1H), 7.36 (d, J=6.5Hz, 1H), 7.60 (t, 114.1, 128.2, 128.7, 129.5, 133.2, 133.5, 137.1, 158.2, 199.5.
J=7.75Hz, 1H), 8.06 (d, J=7.5Hz, 1H), 8.73 (d, J=8.5Hz, 1H), 1-(Naphthalen-1-yl)butan-1-one (4j):31Pale yellow sticky oil,
13CNMR(100 MHz, CDCl3): δ 29.1, 30.5, 30.6, 118.2, 120.5, 1HNMR(500 MHz, CDCl3): δ 1.04 (t, J=7.25Hz, 3H), 1.81-1.85
122.6, 127.6, 129.4, 130.2, 130.5, 133.0, 139.8, 146.1, 153.2, (m, 2H), 3.04 (t, J=7.5Hz, 2H), 7.26-7.53 (m, 2H), 7.57-7.60 (m,
200.3. HRMScalcd.for C14H13O [M+H]+: 197.0966, found: 1H), 7.84 (d, J=7Hz, 1H), 7.88 (d, J=8Hz, 1H), 7.99 (d, J= 8.5 Hz,
197.0962.
1H), 8.55 (d, J=8.5Hz, 1H);13CNMR(100 MHz, CDCl3): δ 14.0,
Propiophenone (4a):4cColorless oil, HNMR(500 MHz, CDCl3): δ 18.3, 44.3, 124.5, 125.9, 126.5, 127.2, 127.9, 128.5, 130.3,
1.23(t, J=7Hz, 3H), 3.00 (q,J = 7.25 Hz, 2H), 7.45 (t, J = 8 Hz, 2H), 132.4, 134.1, 136.7, 205.1.
7.55 (t,J = 7.25 Hz, 1H), 7.96 (d, J=8Hz, 2H); 13CNMR(100 MHz,
1
CDCl3): δ 8.4, 31.9, 128.1, 128.7, 133.0, 137.1, 200.9.
1-Phenylbutan-1-one (4b):16bColorless oil, 1HNMR(500 MHz,
CDCl3): δ 1.01(t, J=7Hz, 3H), 1.75-80 (m, 2H), 2.95 (t, J=7Hz,
2H), 7.44-7.47(m, 2H), 7.53-7.56 (m, 1H), 7.96 (d, J=8Hz, 2H);
13CNMR(100 MHz, CDCl3): δ 14.0, 17.9, 40.7, 128.2, 128.7,
133.0, 137.3, 200.5.
Acknowledgements
Authors acknowledge Prof. AmitabhaSarkar (IACS, Kolkata) for
his generous suggestions and support. M.Y. and T.D. are
thankful to CSIR, India and IACS, Kolkata, respectively for
research fellowships. S.A. acknowledges DST (project no.
SR/S1/OC-101/2012) for financial support.
1-Phenylhexan-1-one (4c):18Pale yellow oil,1HNMR(400 MHz,
CDCl3): δ 0.91(t, J=8.7Hz, 3H), 1.34-1.39 (m, 4H), 1.70-1.78 (m,
2H), 2.95 (t, J=9.2Hz, 2H), 7.45(t, J=9.5Hz, 2H), 7.54 (t, J=9Hz,
1H), 7.96 (d, J=9Hz, 2H); 13CNMR(100 MHz, CDCl3): δ 14.1,
22.6, 24.2, 31.7, 38.7, 128.2, 128.7, 132.9, 137.3, 200.7; HRMS
calcd. for C12H17O [M+H]+: 177.1279, found: 177.1276.
Notes and references
1
(a) H. -G. Franck and J. W. Stadelhofer, Industrial Aromatic
Chemistry; Springer-Verlag: Berlin, 1988. (b) H. Surburg and
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Wiley-VCH: Weinheim, Germany, 2006.
5-Bromo-1-phenylpentan-1-one
(4d):23
White
solid,1HNMR(500 MHz, CDCl3): δ 1.88-2.00 (m, 4H), 3.02 (t,
J=7Hz, 2H), 3.46 (t, J=6.3Hz, 2H), 7.47(t, J=7.5Hz, 2H), 7.57 (t,
J=7.5Hz, 1H), 7.96 (dd, J= 1 Hz, J= 8.25 Hz, 2H); 13CNMR(125
MHz, CDCl3): δ 22.9, 32.4, 33.4, 37.6, 128.2, 128.8, 133.2,
137.0, 199.7.HRMScalcd.for C11H14BrO [M+H]+: 241.0228,
243.0208, found: 241.0224, 243.0218.
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, 129–133; (f) S.
1-Phenyldecan-1-one(4e):22 Colorless oil, 1HNMR(500 MHz,
CDCl3): δ 0.88 (t, J= 6.75 Hz, 3H), 1.27-1.39 (m, 12H), 1.70-1.76
(m, 2H), 2.95 (t, J=7.25Hz, 2H), 7.44 (t, J=7.75Hz, 2H), 7.54 (t,
J=7.5Hz, 1H), 7.95 (d, J=8Hz, 2H); 13CNMR(125 MHz, CDCl3): δ
14.2, 22.8, 24.5, 29.4, 29.5, 29.6, 32.0, 38.7, 128.2, 128.6,
132.9, 137.3, 200.6. HRMS calcd.for C16H25O [M+H]+: 233.1905,
found: 233.1902.
1-Phenyloctadecan-1-one (4f):30 White solid, 1HNMR(500
MHz, CDCl3): δ 0.88 (t, J= 7 Hz 3H), 1.21-1.39 (m, 28H), 1.72-
1.76 (m, 2H), 2.96 (t, J= 7.25 Hz, 1H), 7.46 (t, J= 7.5 Hz, 2H),
7.55 (t, J=7.25 Hz, 1H), 7.96 (d, J= 8.5 Hz, 2H); 13CNMR(100
MHz, CDCl3): δ 14.2, 22.8, 24.6, 29.5, 29.55, 29.6, 29.7, 29.77,
29.8, 29.84, 32.1, 38.8, 128.2 128.7, 133.0, 137.3, 200.7.
2-Ethyl-1-phenylbutan-1-one (4g):24Colorless oil, 1HNMR(500
MHz, CDCl3): δ 0.88 (t,J=7.5Hz, 4H), 1.54-1.59 (m, 2H), 1.77-
1.82 (m, 2H), 3.29-3.32 (m, 1H), 7.47 (t, J=7.5Hz, 2H), 7.56 (t,
J=7.25Hz, 1H), 7.96 (d, J=8.5Hz, 2H); 13CNMR(125 MHz, CDCl3):
δ 12.0, 25.0, 49.4, 128.3, 128.7, 132.9, 138.1, 204.7.
5
, 2219-
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1HNMR(500 MHz, CDCl3): δ 1.36-1.54 (m, 4H), 1.72-1.90 (m,
4H), 3.26 (tt, J= 3Hz, J= 11.25 Hz, 1H), 7.44-7.47 (m, 2H), 7.52-
7.56 (m, 1H), 7.93-7.95 (m, 2H); 13CNMR(125 MHz, CDCl3):
δ26.0, 26.1, 29.6, 45.8, 128.4, 128.7, 132.8, 136.6, 204.0.
7
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New Journal of Chemistry
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DOI: 10.1039/C5NJ01597A
Graphical Abstract Text
The versatile, one-pot synthesis of a series of alkyl aryl ketones is described using ethyl cyanoacetate as a new
acylating agent.