Tautomer-selective derivatives of enolate, ketone and enaminone by addition reaction of picolyl-type anions with nitriles

Article abstract of DOI:10.1016/j.molstruc.2016.09.038

We describe an efficient for the synthesis of compounds of tautomeric β-pyridyl/quinolyl-enol, -ketone, -enaminone, which were finally characterized by standard methods like NMR, IR or SCXRD. The addition reaction of lithiated intermediates of picoline, 2-ethylpyridine and 2-methylquinoline, respectively, with nitriles followed by acid hydrolysis afforded the corresponding tautomeric compounds of enol, ketone and emaminone. Interestingly, treatment of 2-methylpyridine or 2-ethylpyridine with nitriles, respectively, yielded mostly β-pyridyl ketone and enol tautomers without enaminones, while 2-methylquinoline with nitriles gave β-quinolyl ketone and enaminone tautomers without enols. The reaction of 2-benzylpyridine with nitriles was not available under the same conditions.

Full text of DOI:10.1016/j.molstruc.2016.09.038

Accepted Manuscript
Tautomer-selective derivatives of enolate, ketone and enaminone by addition reaction
of picolyl-type anions with nitriles
Jianliang Bai, Peng Wang, Wei Cao, Xia Chen
PII:
S0022-2860(16)30965-6
10.1016/j.molstruc.2016.09.038
MOLSTR 22950
DOI:
Reference:
To appear in: Journal of Molecular Structure
Received Date: 3 June 2016
Revised Date: 10 September 2016
Accepted Date: 13 September 2016
Please cite this article as: J. Bai, P. Wang, W. Cao, X. Chen, Tautomer-selective derivatives of enolate,
ketone and enaminone by addition reaction of picolyl-type anions with nitriles, Journal of Molecular
Structure (2016), doi: 10.1016/j.molstruc.2016.09.038.
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ACCEPTED MANUSCRIPT
Tautomer-selective derivatives of enolate, ketone and enaminone by
addition reaction of picolyl-type anions with nitriles
Jianliang Bai,a Peng Wang,a Wei Caob and Xia Chena
aSchool of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, China
bScientific Instrument Center, Shanxi University, Taiyuan 030006, China
Corresponding author: E-mail address: chenxia@sxu.edu.cn
ABSTRACT
We describe an efficient for the synthesis of compounds of tautomeric
β-pyridyl/quinolyl-enol, -ketone, -enaminone , which were finally characterized by
standard methods like NMR, IR or SCXRD. The addition reaction of lithiated
intermediates of picoline, 2-ethylpyridine and 2-methylquinoline, respectively, with
nitriles followed by acid hydrolysis afforded the corresponding tautomeric
compounds of enol, ketone and emaminone. Interestingly, treatment of
2-methylpyridine or 2-ethylpyridine with nitriles, respectively, yielded mostly
β-pyridyl ketone and enol tautomers without enaminones, while 2-methylquinoline
with nitriles gave β-quinolyl ketone and enaminone tautomers without enols. The
reaction of 2-benzylpyridine with nitriles was not available under the same conditions.
Corresponding author. Tel.: +86-0351-7010588; fax: +86-0351-7011688; e-mail: chenxia@sxu.edu.cn

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Keywords: Pyridyl/Quinolyl; Nitriles; Addition reaction; Ketone; Enol; Enaminones.
1. Introduction
The methods to prepare heterocyclic ketones or enols should be available by the
base-promoted condensation of methyl-heterocycle compounds with the appropriate
esters, nitriles or carboxylic acid chlorides. Although the addition of Grignard
reagents to nitriles has been known for a long time [1], some useful preparations with
bulky reactants are usually required harsh conditions such as refluxing in high boiling
solvents (toluene) for a extended period or large excesses of the Grignard reagents [2].
The addition reactions of nitriles to carbanions have been extensively investigated
to form 1-azaallyls and β-diketiminates [3], after hydrolysis, to afford ketone
compounds [4]. The formation of 1-azaallyls and β-diketiminates involves
nucleophilic attack of carbanion on nitriles to form C-C bond [5]. We have reported
the addition of picolyl/lutidyl lithium with α-hydrogen-free nitriles gave the
pyridyl-substituted 1-azaallyl lithium and their corresponding metal complexes [6];
moreover, the addition reactions of lithium silylquinolylamide with
dimethylcyanamide resulted in quinolylguanidinates [7]. In comparison, little
attention has been devoted to their hydrolysis products which possess a nitrogen
heterocyle aromatic ring as the chelating [N,O] ligands of pyridyl/quinolyl-enolates
[8].
In fact, the most straightforward way to prepare heterocyclic ketones was the
reaction of heterocyclic lithium salt with nitriles followed by acidic hydrolysis [9]. In

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this manner, Bildstein and coworkers reported four compounds of
pyridyl/quinolyl-enolates by addition of α-picolyl/quinolyl-lithium with acetonitrile or
benzonitrile followed by acidic hydrolysis [9b]. These [N,O] ligands exist in three
tautomers: enol, ketone and enaminone, depending on the substituent pattern in the
molecule [9b,10].
To evaluate the scope of the addition and hydrolysis products, a series of aliphatic
and aromatic nitriles were reacted with pyridyl- and quinolyl lithium reagents. Herein,
we report a simple and efficient one pot synthesis of pyridyl/quinolyl ketone and
describe the substituent effect on the tautomeric equilibrium between enol, keton and
enaminone (Scheme 1).
Scheme 1. The reaction of o-substituted pyridine/quinoline with nitriles.
2. Results and discussion
Initially the model reaction of picoline with PhCN was examined under different
conditions (Table 1). As expected, in the solvents like Et2O, hexane and THF, 1c
could be obtained in good yields (Table 1, entries 1-5). Among all the solvents tested,
THF proved to be the most efficient. In this case, the mixture of picoline, BuLi with

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PhCN afforded compound 1c in 80% yield within 6 hours (Table 1, entry 5). Except
BuLi, other types of base reagents were also investigated. ButOK and NaH gave
relatively lower efficiency compared to BunLi (Table 1, entries 6-7).
Table 1. Optimization of the reaction conditions for the synthesis of 1ca
Entry
base
solvent
Et2O
Time
12 h
6 h
Yieldb %
1
2
3
4
5
6
BunLi
BunLi
BunLi
BunLi
BunLi
ButOK
NaH
71
72
45
80
80
32
38
Et2O
Hexane
THF
12 h
12 h
6 h
THF
THF
12 h
12 h
7
THF
a
Reaction conditions: picoline (3.0 mmol), base (3.0 mmol), anhydrous solvent (6
mL), PhCN (3.0 mmol), room temperature.
b Isolated yield.
Under the conditions as for 1c in entry 5 (Table 1), a series of reaction of lithiated
2-substituted pyridine/quinoline with nitriles were carried out, and some of the results
are summarized in Table 2 and Table 3. It was found that different heterocyclic
substrates reacted with nitriles to yield selective tautomeric compounds of enol,
ketone and enaminone under the same reaction conditions (Scheme 1). The reaction
of 2-methylpyridyl anion with RCN gave the tautomeric mixtures of enol and ketone
(1a-1g, Table 2, entries 1-7). However, when the addition of pyridine-2-ylethyl
lithium with nitriles was carried out, ketone forms (2c-2g, Table 2, entries 10-14))

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were found to be dominant in solution or solid. Compound 2c was also obtained by
coupling
of
2-bromopyridine
and
propiophenone
using
di-tert-butylneopentylphosphine and palladium (II) as a catalyst [11]. Thereby, while
reaction of pyridine-2-ylethyl lithium with aliphatic CH3CN and ButCN, respectively,
were proven to be inert under identical conditions, so products 2a and 2b were not
obtained which may be due to the electron-donating group decreasing the
C-eletrophilicity (Table 2, entries 8 and 9). Enaminone tautomers (3a-3f) were more
prominent for 2-sustituted quinolines (Table 3, entries 15-20). 3g could not undergo
the insertion under the identical conditions, which might be attributed to the strong
electron-withdrawing group and steric effects at the ortho benzene ring (Table 3, entry
21).
Table 2. Synthesis of 1 and 2 and their tautomeric compositions
Entry
R
R'
Products Yielda % Enolb % Ketoneb %
1
2
3
4
5
6
7
8
9
10
H
H
H
H
H
H
H
Me
1a
1b
1c
1d
1e
72
83
80
84
90
93
69
NA
NA
73
8
92
88
40
41
73
84
16
‒
But
12
60
59
27
16
84
‒
Ph
o-Tol
p-Tol
p-OMeC6H4 1f
o-CF3C6H4
1g
2a
2b
2c
Me Me
Me But
Me Ph
‒
‒
0
>99

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11
12
13
14
Me o-Tol
Me p-Tol
2d
2e
76
93
84
85
16
0
84
>99
>99
53
Me p-OMeC6H4 2f
Me o-CF3C6H4
2g
0
47
a Isolated yield. bDetermined by 1H NMR (CDCl3)
Table 3. Synthesis of 3 and their tautomeric compositions
Enaminoneb
%
Entry R'
Products Yielda % Ketoneb %
15
16
17
18
19
20
21
Me
3a
3b
3c
3d
3e
62
69
84
87
89
91
NA
18
15
4
82
85
96
97
93
91
‒
But
Ph
o-Tol
p-Tol
3
7
p-OMeC6H4 3f
o-CF3C6H4
3g
9
‒
a Isolated yield. bDetermined by 1H NMR (CDCl3)
When 2-benzylpyridine was used, the reaction did not lead to the formation of the
addition products, excluding a competitive cross-coupling product produced by the
nitriles alone (Scheme 2). The oligomerization of benzonitrile in the presence of
alkyllithium is known reaction [12], and dimerization of methyl-substituted
benzonitrile was reported by Petty [13].

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Scheme 2. The reaction of 2-benzylpyridine with nitriles
The tautomers of enol and ketone were identified by the presence of the H6 signals
1
(usually in CDCl3) in H NMR spectra and an unconjugated keto group in the IR
1
spectra. Figure 1 depicts an overlay of H NMR spectra (300 MHz, CDCl3) of 1c, 2f
and 3d.
Figure 1. Overlay of 1H NMR spectra (300 MHz, CDCl3) of 1c, 2f and3d

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As it can be seen, singlets in the range 3.79-4.54 ppm were assigned to CH2 group
of the ketone and signals in the range 5.27-6.37 were attributed to the CH of the enol
for 1a-1g. Quartets in the range 4.58-5.03 were observed to CH group in 2a-2g, and
singlets in the range of 5.51-6.02 were assigned to CH group in 3a-3f. However, it
is difficult to distinguish the enol and enaminone by comparing their 1H NMR spectra
[8c]. For distinguishing enol and enaminone, 13C NMR spectra would be the best
method based on the difference in carbon chemical shift between C of the enol
(=C-OH) and enaminone (C=O). The values of δc fall in the ranges 185-201 ppm for
the enaminones 3a-3f and156-170 ppm for the enol tautomers 1a-1g. In general, δc
values increase when R becomes more electron-withdrawing for the carbonyl C of
enaminones and enols. The large down-field shift of OH and NH protons at 15-16
ppm was attributed to the strong intramolecular hydrogen bond, in which these
protons are also broadened and that indicated the presence of intermolecular hydrogen
bonds in enols and enaminones.
The proportions of tautomers were determined by integration of the H6 signals
(Figuer 1). It can be seen that the ratios of three forms were sensitive to the
heterocycle and substituent in the molecule. In general, only two of tautomers were
observed in the mixture of respective pyridines (ketone and enol) and quinolines
(ketone and enaminone) [10c]. The strong electron-withdrawing group in the
molecule such as 1g and 2g resulted in more enol form, in contrast, electron-donating
group produced more ketone form.

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IR absorption spectra were in accordance with the assignments of 1H and 13C NMR
shifts. Broad absorption bands were observed in the frequency range 3300-3600 cm-1
due to the strong intramolecular hydrogen bonding interactions of 1a-1g and 3a-3f.
The structures of 1e, 2e and 3d have been confirmed by X-ray single-crystal
diffraction. The different tautomeric equilibria are often paid attention in solution.
However, the molecular structures showed that there was only one tautomer can be
seen in the solid state. The molecular geometries of 1e, 2e and 3d are illustrated in
Figure 2-4 and their selected bond lengths and angles are presented in Table 4.
Figure 2. Molecular structure of 1e.Thermal ellipsoids are drawn at the 30% probability level.
Comparison of their crystal structures, it can be seen that their molecular
geometries are significantly different from each other. For enol 1e and enaminone 3d,
the N1C1C6C7O1 backbone is almost planar and is coplanar with the pyridine (1e)
and quinoline (3d) ring respectively. Their torsion angles of N1,O1-C1-C6-C7 are
4.3(3) and -0.9(4)º for compound 1e, and 4.5(2) and -5.7(2)º for compound 3d,
respectively. However, the N1C1C6C7O1 backbone in ketone 2e is strongly twisted
with the N1,O1-C1-C6-C7 torsion angles being -34.82(17) and 116.08(16)º. In the
N1C1C6C7O1 moiety, the bond lengths N1-C1, C1-C2 and C7-O in 1e and 3d are

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longer and C1-C6 and C6-C7 are shorter compared to those in 2e. That indicates the
π-electron delocalization is present in N1C1C6C7O1 fragment in 1e and 3d. On the
other hand, the C6-C7 bond in 1e is shorter than that in 2e and 3d, forming an obvious
conjugated system between N1C1C6C7O1 and benzene ring. The benzene ring is
almost coplanar with the pyridine ring in 1e, while it is twisted around the C7-C8
bond in 3d. It can be seen the twisting depends on the substituents rather than type of
compound [14]. The intramolecular hydrogen bond O-HꢀꢀꢀN in 1e is almost as long as
that N-HꢀꢀꢀO=C in 3d. Intramolecular hydrogen bonding in 1e and 3d leads to the
formation of a six-membered quasi-ring.
Figure 3. Molecular structure of 2e.Thermal ellipsoids are drawn at the 30% probability level.
Figure 4. Molecular structure of 3d.Thermal ellipsoids are drawn at the 30% probability level.

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Table 4. Selected bond lengths [Å], angles [º] H-bonds [Å]and torsion angles [º] for
1e, 2e and 3d
Geometric parameters
Bond lengths [Å]
C1－N1
1e
2e
3d
1.354(3)
1.399(3)
1.380(3)
1.371(4)
1.383(4)
1.446(3)
1.355(3)
1.351(2)
1.470(3)
1.3317(19)
1.380(2)
1.383(3)
1.362(3)
1.363(3)
1.514(2)
1.518(2)
1.2164(18)
1.492(2)
1.3505(15)
1.4304(17)
1.3402(18)
1.4208(18)
1.4027(16)
1.3908(17)
1.4307(17)
1.2685(15)
1.5062(17)
C1－C2
C2－C3
C3－C4
C4－C5
C1－C6
C6－C7
C7－O1
C7－C8
H-bonds [Å]
O1ꢀꢀꢀH
0.839
-
-
-
-
-
-
N1－H
0.860
-
N1ꢀꢀꢀH
1.817
2.567
N1ꢀꢀꢀ O1
2.615
Bond angles [º]
N1HO1
147.90
-
132.60
N1C1C6
117.6(2)
124.6(2)
121.4(2)
113.6(2)
115.98(14)
109.93(12)
120.44(15)
119.94(15)
120.60(12)
123.44(12)
122.61(12)
118.36(12)
C1C6C7
C6C7O1
C8C7O1
Torsion angles [º]
N1C1C6C7
O1C1C6C7
4.3(3)
-34.82(17)
116.08(16)
4.5(2)
-0.9(4)
-5.7(2)

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3. Conclusions
In conclusion, we have developed an efficient insertion reaction of
pyridyl-/quinolyl-lithium with nitriles for preparing pyridyl-/quinolyl-ketone
compounds. These heterocyclic ketones exist in three tautomers of enol, ketone and
enaminone. The tautomeric equilibria are affected by the substituent in the molecule.
The tautomeric species have been identified from NMR and IR spectra. We noticed
that 1a-1g was in the tautomeric equilibrium with ketone and enol, however, the
ketone was more stable than enol for 2c-2g, and the enaminone was found to be
predominant for 3a-3f. Both enol and enaminone derivatives were stabilized by an
intramolecular hydrogen bond which formed a six-membered quasi-ring. Their anions
are expected to be good σ- and π-donors, like cyclopentadienyl ligands. Based on
above, further studies on the coordination chemistry of this class of ketone ligands
with tautomeric equilibrium and the application of their metal complexes are
presently underway.
4. Experimental
General Information:
All sensitive manipulations were carried out under dry N2 using standard Schlenk
techniques. All reagents purchased from commercial sources were purified by
standard techniques prior to use. Tetrahydrofuran was dried by distilling from
sodium/benzophenone. The compounds 1-(2-Pyridinyl)-2-propanone (1a) [9b],
1-Phenyl-2-(2-pyridinyl)-ethanone (1c) [9b], 1-(2-Quinolinyl)-2-propanone (3a) [10e]

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and 1-Phenyl-2-(2-quinolinyl)-ethanone (3c) [10e] were reported in published papers.
Herein we added some data for future reference. NMR spectra were recorded on a
Bruker AVANCE 600 (1H 600 MHz, 13C 150 MHz) or Bruker AVANCE 300 (1H 300
1
MHz, 13C 75 MHz) at room temperature. The chemical shifts of H and 13C were
referenced to TMS or residual solvent resonances. IR spectra of the compounds were
recorded with a Bruker Tensor 27 ATR-FTIR spectrometer using KBr pellets.
Elemental analyses were performed on an Vario EL III instrument.
Typical procedure for the synthesis of 1a
n
To a solution of 2-methylpyridine (2.79 g, 30 mmol) in 35 mL THF, BuLi (12.4
mL, 2.5 M solution in hexane, 30 mmol) was slowly added at 0 °C with stirring. The
mixture was allowed to warm to room temperature for 4 h, after which acetontrile
(1.61 mL, 31 mmol) was added at 0 °C and then stirred for 6 h at room temperature. A
sulfuric acid of 60% aqueous solution was then added dropwise until a PH of 1 was
reached, and was stirred for 1 d to complete acidic hydrolysis, then neutralized with
saturated aqueous KOH solution. The organic layer was extracted with CH2Cl2 (50
mL×3), then dried over MgSO4 and concentrated by rotary evaporator. This
compound was purified by reduced pressure distillation, resulting in yellow oil of 1a.
1b-2g were purified by reduced pressure distillation. 3a-3f were purified by
recrystallization and chromatography.
1-(2-Pyridinyl)-2-propanone (1a)：
This compound was reported by a published paper [9b]. Because no data of enol have
been reported, we include different data here for future reference. Yield: 2.92 g

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(72%). Bp 45 °C at 3 mbar. 1H NMR (600 MHz, CDCl3, 298 K): δ 2.20 (s, 3H, CH3),
3.89 (s, 2H, CH2), 5.27 (s, 1H, =CH), 6.83-6.92 (m, 2H, pyridyl), 7.16-7.19 (m, 2H,
pyridyl), 7.44-7.52 (m, 1H, pyridyl), 7.63 (d, J = 6.0 Hz 1H, pyridyl), 8.17 (d, J = 8.4
13
Hz, 1H, pyridyl), 8.54 (d, J = 8.4 Hz, 1H, pyridyl), 14.71 (s, 1H, OH). C NMR
(150 MHz, CDCl3, 298 K): δ 22.5, 29.9, 53.0, 95.3, 117.8, 120.2, 121.9, 124.1, 136.6,
144.0, 149.4, 154.7, 167.3 (C-OH), 205.2 (C=O). vmax (KBr): 3418 (OH), 3075, 2912,
2842, 1714 (C=O), 1644 (C=N), 1583 (C=N), 1468, 1432, 1355, 1148, 746 cm-1.
Anal. Calcd for C8H9NO: C, 71.09; H, 6.71; N, 10.36. Found: C, 71.11; H, 6.78; N,
10.42.
3,3-Dimethyl-1-(2-pyridinyl)-2-butanone (1b)：
1
Yellow oil. Yield: 4.41 g (83%). Bp 121 °C at 3 mbar. H NMR (300 MHz, CDCl3,
298 K): δ 1.20 (s, 9H, CH3), 4.01 (s, 2H, CH2), 5.37 (s, 1H, =CH), 6.85-6.91 (m, 2H,
pyridyl), 7.10-7.20 (m, 2H, pyridyl), 7.48 (t, J = 7.8 Hz, 1H, pyridyl), 7.57 (t, J = 7.5
Hz, 1H, pyridyl), 8.15 (d, J = 4.8 Hz, 1H, pyridyl), 8.49 (d, J = 4.5Hz, 1H, pyridyl),
13
15.14 (s, 1H, OH). C NMR (75 MHz, CDCl3, 298 K): 27.0, 28.8, 45.4, 46.7, 91.9,
118.7, 121.6, 122.4, 125.2, 137.0, 137.6, 144.9, 156.3, 212.9 (C=O). vmax (KBr): 3404
(OH), 3034, 2969, 2855, 1717 (C=O), 1635 (C=N), 1603 (C=N), 1480, 1431, 1365,
1275, 1120, 1054, 890, 801, 735 cm-1. Anal. Calcd for C11H15NO: C, 74.54; H, 8.53;
N, 7.90. Found: C, 74.48; H, 8.55; N, 7.92.
1-Phenyl-2-(2-pyridinyl)-ethanone (1c)：
Red oil but slowly solidified. Yield: 4.73 g (80%). Bp 117 °C at 3 mbar. Mp 56-58
1
°C. H NMR (300 MHz, (CD3)2SO, 298 K): 4.54 (s, 2H, CH2), 6.37 (s, 1H, =CH),

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7.12-7.22 (m, 1H, ArH), 7.24-7.30 (m, 1H, ArH), 7.36-7.44 (m, 2H, ArH), 7.49 (t, J =
7.5 Hz, 2H, ArH), 7.61-7.75 (m, 1H, ArH), 7.77-7.85 (m, 1H, ArH), 8.01 (d, J = 7.8
Hz, 2H, ArH), 8.39 (d, J = 3.9 Hz, 1H, ArH), 8.46 (d, J = 3.3 Hz, 1H, ArH), 15.38 (s,
1
1H, OH). H NMR (300 MHz, CDCl3, 298 K): δ 4.40 (s, 2H, CH2), 5.98 (s, 1H,
=CH), 6.84 (t, J = 6.0 Hz, 1H, ArH), 6.94 (d, J = 8.1 Hz, 1H, ArH), 7.04 (t, J = 6.0
Hz, 1H, ArH), 7.19 (d, J = 7.8 Hz, 1H, ArH), 7.29-7.37 (m, 5H, ArH), 7.42-7.56 (m,
3H, ArH), 7.75 (d, J = 6.9 Hz, 2H, ArH), 7.96 (d, J = 7.8 Hz, 2H, ArH), 8.16 (d, J =
13
4.8 Hz, 1H, ArH), 8.46 (d, J = 4.2 Hz, 1H, ArH), 15.23 (s, 1H, OH). C NMR (75
MHz, (CD3)2SO, 298 K): δ 48.5, 94.6, 119.9, 122.7, 126.0, 128.3, 129.3, 129.6,
130.1, 130.3, 134.1, 136.8, 137.3, 137.4, 138.9, 145.1, 149.9 , 156.6, 158.6, 164.0
(C-OH), 197.9 (C=O). vmax (KBr): 3420 (OH), 1648 (C=O), 1590 (C=N), 1545
(C=N), 1420, 1378, 1280, 1144, 806, 751, 678 cm-1. Anal. Calcd for C13H11NO: C,
79.16; H, 5.62; N, 7.10. Found: C, 79.07; H, 5.71; N, 7.04.
1-(2-Methylphenyl)-2-(2-pyridinyl)-ethanone (1d)：
Yellow oil but slowly solidified. Yield: 5.32 g (84%). Bp 135 °C at 3 mbar. 1H NMR
(300 MHz, (CD3)2SO, 298 K): δ 2.39 (s, 3H, CH3), 2.50 (s, 3H, CH3), 4.45 (s, 2H,
CH2), 5.76 (s, 1H, =CH), 7.09-7.11 (m, 1H, ArH), 7.12-7.14 (m, 1H, ArH), 7.20-7.32
(m, 4H, ArH), 7.35-7.45 (m, 4H, ArH), 7.69-7.76 (m, 2H, ArH), 7.79-7.92 (m, 2H,
ArH), 8.37 (d, J = 5.1 Hz, 1H, ArH), 8.46 (d, J = 5.1 Hz, 1H, ArH), 15.25 (s, 1H,
13
OH). C NMR (75 MHz, (CD3)2SO, 298 K): δ 19.6, 20.0, 49.7, 96.6, 118.1, 120.8,
121.1, 123.7, 125.0, 125.1, 127.3, 128.0, 128.3, 130.0, 130.6, 130.9, 134.8, 135.8,
136.6, 136.8, 137.2, 143.3, 148.4, 155.0, 157.0, 166.8 (C-OH), 200.1 (C=O). vmax

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(KBr): 3422 (OH), 3002, 2933, 2870, 1644 (C=O), 1593 (C=N), 1564 (C=N), 1508,
1442, 1163, 1054, 948, 847, 728 cm-1. Anal. Calcd for C14H13NO: C, 79.59; H, 6.20;
N,6.63. Found: C,79.64; H, 6.27; N, 6.68.
1-(4-Methylphenyl)-2-(2-pyridinyl)-ethanone (1e)：
Yellow oil but slowly solidified. Yield: 5.70 g (90%). Bp 142 °C at 3 mbar. Mp 66-69
1
°C. H NMR (300 MHz, CDCl3, 298 K): δ 2.32 (s, 3H, ArCH3), 4.41 (s, 2H, CH2),
5.96 (s, 1H, =CH), 6.85-6.89 (m, 1H, ArH), 6.95 (d, J = 8.1 Hz, 1H, ArH), 7.07-7.25
(m, 4H, ArH), 7.49-7.59 (m, 1H, ArH), 7.65 (d, J = 7.8 Hz, 1H, ArH), 7.88 (d, J =
8.1 Hz, 1H, ArH), 8.18 (d, J = 4.8 Hz, 1H, ArH), 8.48 (d, J = 4.5 Hz, 1H, ArH),
15.32 (s, 1H, OH). 13C NMR (75 MHz, CDCl3, 298 K): δ 22.1, 22.4, 49.0, 94.2,
118.9, 122.2, 122.6, 125.0, 126.2, 129.6, 130.1, 134.8, 137.4, 137.8, 144.9, 150.1,
156.1, 197.2 (C=O). vmax (KBr): 3428 (OH), 2929, 2855, 1643 (C=O), 1586 (C=N),
1537 (C=N), 1513, 1455, 1382, 940, 808, 735 cm-1. Anal. Calcd for C14H13NO: C,
79.59; H, 6.20; N, 6.63. Found: C, 79.48; H, 6.33; N, 6.74.
1-(4-Methoxyphenyl)-2-(2-pyridinyl)-ethanone (1f)：
Yellow oil but slowly solidified. Yield: 6.33 g (93%). Bp 153 °C at 3 mbar. Mp 85-87
1
°C. H NMR (300 MHz, CDCl3, 298 K): δ 3.71 (s, 3H, OCH3), 4.33 (s, 2H, CH2),
5.86 (s, 1H, =CH), 6.78 (d, J = 8.4 Hz, 2H, ArH), 6.88 (d, J = 8.1 Hz, 2H, ArH), 7.04
(t, J = 6.0 Hz, 1H, ArH), 7.17 (d, J = 7.8 Hz, 1H, ArH), 7.41 (d, J = 7.8 Hz, 1H,
ArH), 7.48-7.53 (m, 2H, ArH), 7.66 (d, J = 8.4 Hz, 2H, ArH), 7.92 (d, J = 8.4 Hz,
1H, ArH), 8.09 (d, J = 4.8 Hz, 1H, ArH), 8.44-8.53(m, 1H, ArH), 13C NMR (150
MHz, CDCl3, 298 K): δ 51.0, 58.1, 58.3, 95.5, 116.2, 120.8, 124.2, 124.7, 127.1,

ACCEPTED MANUSCRIPT
129.8, 131.9, 132.4, 133.8, 134.7, 139.4, 139.9, 146.7, 152.3, 158.4, 161.5, 163.5,
166.5 (C-OH), 198.2 (C=O) ppm. vmax (KBr): 3424 (OH), 2978, 2912, 2847, 1627
(C=O), 1584 (C=N), 1546 (C=N), 1504, 1455, 1234, 1177, 1054, 874, 792, 726 cm-1.
Anal. Calcd for C14H13NO2: C, 73.99; H, 5.77; N,6.16. Found: C, 74.12; H, 5.68; N,
6.14.
2-(2-Pyridinyl)-1-[2-(trifluoromethyl)pheny- l]-ethanone (1g)：
Red oil. Yield: 5.48 g (69%). Bp 135 °C at 3 mbar. 1H NMR (300 MHz, CDCl3, 298
K): δ 4.16 (s, 2H, CH2), 5.39 (s, 1H, =CH), 6.69 (d, J = 7.5Hz, 2H, ArH), 6.92 (d, J =
6.6 Hz, 1H, ArH), 7.05 (d, J = 6.0 Hz, 1H, ArH), 7.20 (d, J = 6.9 Hz, 1H, ArH), 7.29
(d, J = 6.0 Hz, 1H, ArH), 7.35 (d, J = 7.2 Hz, 1H, ArH), 7.46 (d, J = 6.9 Hz, 1H,
ArH), 7.91 (d, J = 6.9 Hz, 1H, ArH), 8.23-8.32 (m, 1H, ArH), 15.33 (s, 1H, OH). 13C
NMR (150 MHz, CDCl3, 298 K): δ 32.6, 54.9, 100.2, 100.5, 120.5, 121.2, 124.3,
125.1, 129.2, 129.3, 130.4, 130.6, 131.3, 131.6, 133.0, 133.2, 134.5, 134.6, 138.5,
139.5, 140.3, 141.8, 142.4, 145.6, 150.4, 152.2, 156.8, 160.5, 162.5, 170.7 (C-OH),
203.4 (C=O). vmax (KBr): 3420 (OH), 1645 (C=O), 1594 (C=N), 1568 (C=N), 1472,
1357, 1264, 1080, 937, 807, 735 cm-1. Anal. Calcd for C14H10F3NO: C, 63.40; H,
3.80; N, 5.28. Found: C, 63.32; H, 3.77; N, 5.33.
1-Phenyl-2-(2-pyridinyl)-1-propanone (2c)：
Yellow oil but slowly solidified. Yield: 4.62 g (73%). Bp 123 °C at 3 mbar. Mp 65-68
°C. 1H NMR (300 MHz, (CD3)2SO, 298 K): δ 1.41 (d, J = 6.9 Hz, 3H, CH3), 5.03 (m,
1H, CH), 7.14-7.16 (m, 1H, ArH), 7.18-7.43 (m, 3H, ArH), 7.48-7.53 (m, 1H, ArH),
7.53-7.74 (m, 1H, ArH), 8.38 (m, 1H, ArH). 13C NMR (75 MHz, (CD3)2SO, 298 K): δ

ACCEPTED MANUSCRIPT
16.8, 48.6, 121.1, 121.8, 127.6, 132.1, 135.6, 136.4, 148.5, 160.4, 198.3 (C=O). vmax
(KBr): 3051, 2994, 2929, 1685 (C=O), 1594 (C=N), 1578 (C=N), 1431, 1325, 1226,
1071, 956, 792, 743, 702 cm-1. Anal. Calcd for C14H13NO: C, 79.59; H, 6.20; N, 6.63.
Found: C,79.44; H, 6.14; N, 6.74.
1-(2-Methylphenyl)-2-(2-pyridinyl)-1-propanone (2d)：
1
Yellow oil. Yield: 5.13 g (76%). Bp 138 °C at 3 mbar. H NMR (300 MHz, CDCl3,
298 K): δ 1.48 (d, J = 6.9 Hz, 3H, CH3), 1.68 (s, 3H, CH3), 2.27 (s, 3H, ArCH3), 2.36
(s, 3H, ArCH3), 4.70 (m, 1H, CH), 6.95-7.19 (m, 6H, ArH), 7.46 (t, J = 7.5 Hz, 1H,
ArH), 7.60 (d, J = 6.9 Hz, 1H, ArH), 8.27 (s, 1H, ArH), 8.40 (d, J = 3.9 Hz, 1H, ArH),
15.96 (s, 1H, OH). 13C NMR (75 MHz, CDCl3, 298 K): δ 15.5, 18.6, 20.4, 22.2,
54.1,118.2,118.7,119.3, 119.8, 120.1, 122.9, 123.4, 126.6, 129.3, 129.7,131.2, 132.1,
137.8, 138.5, 139.1, 139.5, 145.5, 150.6, 161.8, 164.2 (C-OH), 204.6 (C=O). vmax
(KBr): 3418 (OH), 2908, 1658 (C=O), 1621 (C=N), 1586 (C=N), 1460, 1311, 1048,
947, 792, 743, 686 cm-1. Anal. Calcd for C15H15NO: C, 79.97; H, 6.71; N, 6.22.
Found: C, 79.75; H, 6.59; N, 6.18.
1-(4-Methylphenyl)-2-(2-pyridinyl)-1-propanone (2e)：
Yellow oil but slowly solidified. Yield: 6.28 g (93%). Bp 144 °C at 3
1
mbar. Mp 70-71 °C. H NMR (300 MHz, CDCl3, 298 K): δ 1.47 (d, J =
6.9 Hz, 3H, CH3), 2.18 (s, 3H, ArCH3), 4.86 (m, 1H, CH), 6.92 (d, J =
5.1 Hz, 1H, ArH), 7.01 (d, J = 7.8 Hz, 2H, ArH), 7.13 (d, J = 7.8 Hz, 1H,
ArH), 7.41 (m, 1H, ArH), 7.85 (d, J = 7.8 Hz, 1H, ArH), 8.40 (d, J = 5.1
Hz, 1H, ArH). 13C NMR (75 MHz, CDCl3, 298 K): δ 18.3, 21.8, 50.8,

ACCEPTED MANUSCRIPT
122.1, 122.2, 129.4, 134.2, 137.2, 143.9, 161.5, 199.2 (C=O) ppm. vmax
(KBr): 2929, 1685 (C=O), 1603 (C=N), 1562 (C=N), 1431, 1341, 1234,
1054, 956, 850, 801, 759 cm-1 . Anal. Calcd for C15H15NO: C, 79.97; H,
6.71; N, 6.22. Found: C, 79.81; H, 6.63; N, 6.31.
1-(4-Methoxyphenyl)-2-(2-pyridinyl)-1-propanone (2f)：
1
Yellow oil. Yield: 6.08 g (84%). Bp 158 °C at 3 mbar. H NMR (300 MHz, CDCl3,
298 K): δ 1.56 (d, J = 6.9Hz, 3H, CH3), 3.79 (s, 3H, OCH3), 4.90 (m, 1H, CH), 6.84
(d, J = 8.7 Hz, 2H, ArH), 7.07 (t, J = 6.0 Hz,1H, ArH), 7.23 (d, J = 7.8 Hz,1H, ArH),
7.55 (t,J = 7.8 Hz,1H, ArH), 8.01 (d, J = 8.7 Hz, 2H, ArH), 8.53 (d, J = 5.1 Hz, 1H,
ArH). 13C NMR (75 MHz, CDCl3, 298 K): δ 18.2, 50.6, 55.6, 114.0, 122.1, 129.7,
131.5, 137.1, 149.8, 161.7, 163.6, 198.2 (C=O). vmax (KBr): 2912, 1705 (C=O), 1635
(C=N), 1594 (C=N), 1471, 1322, 1128, 848, 752, 712 cm-1. Anal. Calcd for
C15H15NO2: C, 74.67; H, 6.27; N, 5.81. Found: C, 74.45; H, 6.22; N, 5.77.
2-(2-Pyridinyl)-1-[2-(trifluoromethyl)phenyl]-1-propanone (2g)：
Red oil but slowly solidified. Yield: 7.12 g (85%). Bp 138 °C at 3 mbar. Mp 72-74
°C. 1H NMR (300 MHz, CDCl3, 298 K): δ 1.56 (d, J = 7.2 Hz, 3H, CH3), 1.66 (s, 3H,
CH3), 4.56-4.63 (m, 1H, CH), 7.03-7.07 (m, 2H, ArH), 7.09-7.13 (m, 2H, ArH),
7.13-7.55 (m, 3H, ArH), 7.58 (d, J = 8.1 Hz, 2H, ArH), 7.70 (t, J = 8.1 Hz, 2H, ArH),
8.31 (d, J = 4.8 Hz, 1H, ArH), 8.47 (d, J = 4.5 Hz, 1H, ArH), 16.32 (s, 1H, OH). 13C
NMR (150 MHz, CDCl3, 298 K): δ 17.6, 19.9, 57.0, 103.3, 121.6, 122.0, 124.8,
125.6, 127.4, 127.8, 129.1, 129.5, 130.9, 131.3, 132.9, 133.5, 134.6, 134.9, 140.5,
146.9, 152.3, 162.6, 164.1 (C-OH), 206.3 (C=O). vmax (KBr): 3436 (OH), 2936, 1643

ACCEPTED MANUSCRIPT
(C=O), 1603 (C=N), 1553 (C=N), 1488, 1316, 1177, 1005, 931, 792, 768 cm-1. Anal.
Calcd for C15H12F3NO: C, 64.51; H, 4.33; N, 5.02. Found: C, 64.65; H, 4.38; N, 4.96.
1-(2-Quinolinyl)-2-propanone (3a)：
Yellow powder. Yield: 3.44 g (62%). NMR spectra data is consistent with literature
values.2 vmax (KBr): 3354 (OH), 2912, 2855, 1635 (C=O), 1586 (C=N), 1563 (C=N),
1455, 1414, 1357, 1217, 1177, 1152, 940, 833, 726 cm-1.
3,3-Dimethyl-1-(2-quinolinyl)-2-butanone (3b)：
This was recrystallized from (CH2Cl2/Hexane=1/1) then purified by chromatography
(petroleum ether/ethyl acetate=8/1) to afford a yellow powder. Yield: 4.70 g (69%).
1
Mp 71-72 °C. H NMR (300 MHz, CDCl3, 298 K): δ 1.24 (s, 9H, CH3), 5.51 (s, 1H,
CH), 6.72 (d, J = 9.0 Hz, 1H, ArH), 7.21 (t, J = 7.5 Hz, 1H, ArH), 7.37 (d, J = 8.1 Hz,
2H, ArH), 7.47 (t, J = 7.5 Hz, 1H, ArH), 7.56 (d, J = 9.0 Hz, 1H, ArH), 15.28 (s, lH,
NH) (enaminone-form). 13C NMR (150 MHz, CDCl3, 298 K): δ 28.1, 40.7, 88.1,
117.9, 122.4, 123.0, 123.2, 127.5, 130.7, 135.6, 137.9, 153.8, 200.5 (C=O)
(enaminone-form). δ 26.4, 44.9, 47.2, 122.3, 126.2, 126.9, 127.6, 129.0, 129.4, 136.1,
147.9, 156.2, 212.4 (C=O) (ketone-form). vmax (KBr): 3421 (NH), 3044, 2962, 1635
(C=O), 1578(C=N), 1553 (C=N), 1471, 1406, 1357, 1210, 1136, 883, 808, 743 cm-1.
Anal. Calcd for C15H17NO: C, 79.26; H, 7.54; N, 6.16. Found: C, 79.02; H, 7.66; N,
6.08.
1-(2-Methylphenyl)-2-(2-quinolinyl)-ethanone (3d)：
1
Yellow powder. Yield: 6.81 g (87%). Mp 140-141°C. H NMR (300 MHz, CDCl3,
298 K): δ 2.46 (s, 3H, ArCH3), 5.58 (s, 1H, CH), 6.72 (d, J = 9.3 Hz, 1H, ArH),

ACCEPTED MANUSCRIPT
7.16-7.20 (m, 4H, ArH), 7.45 (d, J = 7.2 Hz, 4H, ArH), 7.56 (d, J = 9.0 Hz, 1H, ArH),
15.34 (s, lH, NH) (enaminone-form).13C NMR (150 MHz, CDCl3, 298 K): δ 20.3,
93.8, 118.1, 122.1, 123.2, 123.6, 125.4, 127.6, 128.8, 130.8, 130.9, 135.7, 136.1,
137.7, 141.6, 153.6, 189.3 (C=O) (enaminone-form) . vmax (KBr): 3428 (NH), 3060,
2962, 2929, 1635 (C=O), 1578 (C=N), 1546 (C=N), 1447, 1406, 1341, 1217, 1185,
1071, 980, 817, 751 cm-1. Anal. Calcd for C18H15NO: C, 82.73; H, 5.79; N, 5.36.
Found: C, 82.58; H, 5.87; N, 5.28.
1-(4-Methylphenyl)-2-(2-quinolinyl)-ethanone (3e)：
1
Yellow powder. Yield: 6.97 g (89%). Mp 173-175 °C. H NMR (300 MHz, CDCl3,
298 K): δ 2.41 (s, 3H, ArCH3), 6.05 (s, 1H, CH), 6.86 (d, J = 6.9Hz, 1H, ArH), 7.25
(d, J = 7.2 Hz, 3H, ArH), 7.44-7.55 (m, 3H, ArH), 7.64 (d, J = 9.3 Hz, 1H, ArH),
7.87(d, J = 7.8 Hz, 2H, ArH), 15.65 (s, lH, NH) (enaminone-form). 13C NMR (75
MHz, CDCl3, 298 K): δ 21.6, 89.7, 118.1, 122.5, 123.3, 123.7, 126.8, 127.7, 129.1,
129.6, 131.1, 136.1, 137.2, 137.9, 140.9, 154.1, 184.5 (C=O) (enaminone-form).
vmax(KBr): 3411 (NH), 3051, 2929, 1627 (C=O), 1578 (C=N), 1546 (C=N), 1455,
1414, 1332, 1185, 1136, 964, 817,735 cm-1. Anal. Calcd for C18H15NO: C, 82.73; H,
5.79; N, 5.36. Found: C, 82.86; H, 5.64; N, 5.38.
1-(4-Methoxyphenyl)-2-(2-quinolinyl)-ethanone (3f)：
1
Yellow powder. Yield: 7.60 g (91%). Mp 156-157 °C. H NMR (300 MHz, CDCl3,
298 K): δ 3.86 (s, 3H, OCH3 ), 6.02 (s, 1H, CH), 6.84 (d, J = 9.3 Hz, 1H, ArH), 6.96
(d, J = 8.1 Hz, 2H, ArH), 7.20-7.26 (m, 2H, ArH), 7.42-7.61 (m, 4H, ArH), 7.95 (d, J
= 9.0 Hz, 1H, ArH), 15.54 (s, lH, NH) (enaminone-form). 13C NMR (75 MHz, CDCl3,

ACCEPTED MANUSCRIPT
298 K): δ 55.4, 89.2, 113.6, 117.8, 122.5, 123.5, 127.6, 128.5, 131.0, 132.7, 135.9,
137.8, 153.8, 161.7, 169.6, 184.2 (C=O) (enaminone-form). vmax (KBr): 3420 (NH),
3011, 2978, 2929, 1635 (C=O), 1594 (C=N), 1546 (C=N), 1455, 1420, 1325, 1250,
1168, 1022, 956, 817,743 cm-1. Anal. Calcd for C18H15NO2: C, 77.96; H, 5.45; N,
5.05. Found: C, 77.82; H, 5.38; N, 4.98.
X-ray crystallography：
X-ray diffraction data were collected on a Bruker D8 Venture CCD diffractometer
using graphite-monochromated Mo Kα radiation (λ = 0.71073 Å). The structures were
solved by direct methods [15]. All non-H atoms were refined anisotropically and the
H atoms were included in calculated positions [15]. CCDC 1437358 (1e), 1437359
(2e) and 1411757 (3d) contains the supplementary crystallographic data which can be
obtained free of charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif. Crystallographic data for compounds 1e, 2e
and 3d are summarized in Table 5.
Table 5. Details of the X-ray structure determinations of compounds 1e, 2e and 3d
Compound
1e
2e
3d
Formula
C14H13NO
211.25
C15H15NO
225.28
C18H15NO
261.31
Formula weight
Crystal system
Space group
Orthorhombic
P212121
Orthorhombic
P212121
Monoclinic
P21/c
Colour of crystal
Yellow
Yellow
Yellow
a(Å)
7.4849(3)
11.7102(5)
25.6784(11)
90
6.8411(4)
10.6073(7)
17.5834(11)
90
7.6693(3)
14.5236(5)
12.2223(4)
90
b(Å)
c(Å)
α(°)
β(°)
90
90
92.0500(10)
90
γ(°)
V(Å3)
90
90
2250.70(16)
200(2)
8
1275.95(14)
282(2)
4
1360.52(8)
296(2)
4
Temperature (K)
Z
D(gcm–3)
1.247
1.173
1.276
Crystal size (mm)
0.30×0.18×
0.15
0.30×0.25×
0.18
0.48×0.40×
0.28
ꢀ (mm–1)
0.079
0.073
0.079

ACCEPTED MANUSCRIPT
θ range (°)
2.83-25.04
17446
293
3.01-25.05
9682
2.18-25.05
7684
Reflections collected
Number of parameters
F(000)
157
183
896
480
552
Goodness-of-fit onF2
1.037
1.067
1.069
Final R indices [I>2σ(I)]
R1
R1 = 0.0464
R1 = 0.0322
R1 = 0.0352
wR2
wR2 = 0.0958
wR2 = 0.0707
wR2 = 0.0949
R indices (all data)
R1
R1 = 0.0768
R1 = 0.0411
R1 = 0.0407
wR2
wR2 = 0.1085
wR2 = 0.0762
wR2 = 0.1001
Acknowledgements
We thank the National Natural Science Foundation of China (grant no. 21072120),
Shanxi Patent Promotion Implementation Project (20161001), Shanxi International
Science and Technology Cooperation Program (2015081050) and Open Research
Fund of State Key Laboratory of Polymer Physics and Chemistry, Changchun
Institute of Applied Chemistry, Chinese Academy of Sciences (201408).
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Highlights
An efficient insertion reaction of pyridyl-/quinolyl-lithium with nitriles for preparing
pyridyl-/quinolyl-ketone compounds was reported.
The tautomeric equilibria were affected by the substituent in the molecule.
A useful way to determine the structures of β-pyridyl-/quinolyl-enol, -ketone, -enaminone
tautomers have been described.