Microwave promoted one-pot preparation of fluorinated propargylamines and their chemical transformation

Article abstract of DOI:10.1016/j.jfluchem.2011.08.005

A series of fluorinated propargylamines have been synthesized from the one-pot three-component reaction of fluorobenzaldehyde, aniline and phenylacetylene under solvent-free and microwave irradiation. The fluorinated propargylamines were then further transformed to chalcones or quinoline derivatives respectively depending on the different structures of propargylamines.

Full text of DOI:10.1016/j.jfluchem.2011.08.005

Journal of Fluorine Chemistry 133 (2012) 139–145
Contents lists available at ScienceDirect
Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
Microwave promoted one-pot preparation of fluorinated propargylamines and
their chemical transformation
*
Xiao-Lei Chen, Jian-Min Zhang , Wen-Li Shang, Bei-Qiong Lu, Jian-An Jin
Department of Chemistry, School of Science, Shanghai University, Shanghai 200444, China
A R T I C L E I N F O
A B S T R A C T
Article history:
A series of fluorinated propargylamines have been synthesized from the one-pot three-component
reaction of fluorobenzaldehyde, aniline and phenylacetylene under solvent-free and microwave
irradiation. The fluorinated propargylamines were then further transformed to chalcones or quinoline
derivatives respectively depending on the different structures of propargylamines.
ß 2011 Elsevier B.V. All rights reserved.
Received 18 May 2011
Received in revised form 31 July 2011
Accepted 3 August 2011
Available online 10 August 2011
This paper is dedicated to
Professor Wei-Yuan Huang on the
occasion of his 90th birthday.
Keywords:
Fluorinated propargylamines
One-pot three-component reaction
Chalcones
Quinoline derivatives
Microwave irradiation
1. Introduction
free one-pot three-component reaction to 2-pentauorophenylqui-
noline derivatives was reported by our group [10].
It is known that propargylamines are prepared in one-pot
reaction of benzaldehyde, aniline and phenylacetylene under the
conventional thermal conditions or microwave irradiation condi-
tions. Alternatively addition reactions of phenylacetylenes to
imines also provide the propargylamines and their enantioselec-
tive versions are the recent topic [1]. In general, thermal conditions
require long reaction time [2] and the use of poisonous organic
solvents [3]. We have recently reported the procedure under the
solvent free and short reaction time conditions [4].
According to previous reports, corresponding quinoline deri-
vatives were formed after chemical transformation of propargy-
lamines [11]. However, it was noticed that propargylamines
obtained from anilines with electron withdrawing groups have not
been studied. Thus, in this paper we investigated the chemical
transformation of fluorinated propargylamines with different
substituent groups.
2. Results and discussion
There are many literature reports about the synthesis of
quinoline derivatives, such as hafnium (IV)-catalyzed one-pot
synthesis of substituted quinolines in fluorous media [5], iron-
catalyzed tandem reactions of aldehydes, terminal alkynes, and
primary amines [6], one-pot coupling-addition-cyclocondensa-
tion-sulfur extrusion sequence [7], nickel-catalyzed cyclization of
2-iodoanilines with aroylalkynes [8], and the reaction of 2-
aminobenzophenone and ethyl acetoacetate in the presence of
phosphotungstic acid [9]. In 2004, microwave promoted solvent-
A series of fluorinated propargylamines were prepared by one-
pot three-component condensation reaction of fluorobenzalde-
hyde, aniline and phenylacetylene, using CuCl as catalyst, in N2
atmosphere, under microwave irradiation (750 W) (Scheme 1 and
Table 1) [4].
Different type of products were obtained when the fluorinated
propargylamines 4 were further irradiated by microwave in air, in
the presence of montmorillonite doped with CuCl. That is, it was
found that N-phenyl propargylamines 4ba and 4ca gave the
corresponding quinoline derivatives 6 in 72% and 75% yield
respectively, while all of the other N-nitrophenyl propargylamines
gave two products, fluorinated chalcones 5 and the nitroanilines 2.
(Scheme 2 and Table 2)
* Corresponding author. Tel.: +86 21 66133801; fax: +86 21 66133801.
E-mail address: jmzhang@shu.edu.cn (J.-M. Zhang).
0022-1139/$ – see front matter ß 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2011.08.005

140
X.-L. Chen et al. / Journal of Fluorine Chemistry 133 (2012) 139–145
R1
NH2
NH
CuCl(30%mol.),N2
Ph
ArfCHO
Arf
MW,neat
750W
R1
Ph
3
4
1
2
R1=H
m-NO2
p-NO2
1a
1b
1c
1d
1e
1f
Arf=2-FC6H4
3-FC6H4
2a
2b
2c
4-FC6H4
2,3-F2C6H3
2,4-F2C6H3
2,5-F2C6H3
3,4-F2C6H3
1g
Scheme 1. Synthesis of fluorinated propargylamines 4.
R1
R1 = H or Me[11]
CuCl-Mont.
N
Arf
CuCl-Mont.
MW, air
MW, air
NH
6
NH2
O
Arf
R1 = NO2
Arf
CuCl-Mont.
MW, air
O2N
2
4
5
Scheme 2. Chemical transformation of 4 to 5 or 6.
As shown in entries 4–14, yields of fluorinated chalcones and
First, the effect of irradiation power was briefly investigated. As
a model reaction, formation of 6cc was chosen. It was observed
that yield of 6cc was gradually increased by increasing the
irradiation power up to 300 W, but it became lower when the
microwave power exceeded 300 W. Thus, 300 W was chosen as the
optimum irradiation power for 6cc. Then the effect of microwave
irradiation time was studied, and 3 min was found to be the
optimized reaction time for the formation of 6cc. On the basis of
these optimized conditions, various combinations of fluoroben-
zaldehydes and anilines were employed for the three-component
nitroanilines were moderate to good. In addition, the same results
were obtained when unpurified fluorinated propargylamines were
used.
Next, we examined the direct synthesis of the quinoline
derivative 6 by the one-pot three-component reactions. Under the
atmospheric, microwave irradiation and solvent-free conditions,
quinoline derivative 6 was obtained, when fluorobenzaldehyde
1a–1g, aniline 2a–2c and phenylacetylene 3 were mixed with
montmorillonite doped with CuCl. (Scheme 3)
Table 1
Table 2
One-pot synthesis of propargylamines 4 under microwave irradiation conditiona.
Chemical transformation of 4 under microwave irradiation conditiona.
Entry
Aldehyde 1
Amine 2
Time (min)
Product
Yield (%)b
Entry
4
Power (W)
Time (min)
Product and yield (%)b
1
2
1b
1c
1a
1b
1c
1d
1e
1f
2a
2a
2c
2c
2c
2c
2c
2c
2c
2b
2b
2b
4
4
4
2
2
5
4
4
4
2
2
2
4ba
4ca
4ac
4bc
4cc
4dc
4ec
4fc
45
46
41
89
50
45
66
34
35
43
78
53
1
2
4ba
4ca
4ac
4bc
4cc
4dc
4ec
4fc
450
450
600
600
450
750
750
750
750
600
600
450
6
6
6ba (72)
6ca (75)
5a (41)
5b (50)
5c (78)
5d (67)
5e (52)
5f (37)
5g (55)
5a (40)
5b (47)
5c (73)
–
–
3
3
6
2c (30)
2c (34)
2c (70)
2c (63)
2c (48)
2c (20)
2c (29)
2b (34)
2b (46)
2b (68)
4
4
6
5
5
10
3
6
6
7
7
3
8
8
3
9
1g
1a
1b
1c
4gc
4ab
4bb
4cb
9
4gc
4ab
4bb
4cb
5
10
11
12
10
11
12
6
6
10
a
a
Using CuCl as catalyst, in N2 atmosphere, power 750 W, and the molar ratio of 1/
2/3/CuCl = 1:1.2:1.5:0.3.
Montmorillonite clay (about 0.7 g based on 1 mmol propargylamine) doped
with CuCl, open in air.
b
b
Isolated yield based on 1.
Isolated yield based on 4.

X.-L. Chen et al. / Journal of Fluorine Chemistry 133 (2012) 139–145
141
Scheme 3. Synthesis of quinoline derivatives 6.
Scheme 4. Possible mechanism for the chemical transformation of 4 to 5.
reactions with phenylacetylene. Results are summarized in Table
3.
The mechanism of transformation of N-phenylpropargylamine
4ba and 4ca into quinoline derivative 6 is involving the air
oxidation step shown in Scheme 5 as previous reported [11].
The preparation of N-arylated propargylamines and their
transformation into quinoline derivatives or chalcone derivatives
are summarized in Scheme 6.
When R1 is CH3 or H, the following cyclization reaction of
propargylamines gave quinoline derivatives; however, when R1 is
an electron drawing NO2 group, it afforded chalcones and anilines.
The results demonstrated that catalyst and nitrogen atmosphere
The formation of chalcone derivative and the nitroaniline from
the N-nitrophenylated propargylamine would possibly be
explained by considering that nitroaniline would act as a good
leaving group which contributed to the generation of the allenic
cation species. The subsequent reaction with water proceeded
quickly to yield chalcone. Montmorillonite doped with CuCl played
an important role for the activation of the nitroaniline by the
coordination as shown in Scheme 4.
Table 3
One-pot reaction to prepare quinoline derivativesa.
Entry
Aldehyde 1
Aniline 2
Power (W)
Time (min)
Product
Yield (%)b
1
2
1b
1c
1a
1b
1c
1d
1e
1f
2a
2a
2c
2c
2c
2c
2c
2c
2c
2b
2b
2b
300
300
300
300
300
300
300
300
300
450
450
450
5
4
5
4
3
3
3
3
3
8
6
6
6ba
6ca
6ac
6bc
6cc
6dc
6ec
6fc
61
64
78
80
86
75
80
78
76
68
72
74
3
4
5
6
7
8
9
1g
1a
1b
1c
6gc
6ab
6bb
6cb
10
11
12
a
Montmorillonite clay (about 1.2 g based on 1 mmol benzaldehyde) doped with CuCl, open air, and the molar ratio of 1/2/3/CuCl = 1:1:2:0.3.
b
Isolated yield based on aldehyde 1.

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X.-L. Chen et al. / Journal of Fluorine Chemistry 133 (2012) 139–145
Scheme 5.
Scheme 6.
Scheme 7. Possible mechanism of one-pot synthesis of quinoline derivatives.
are necessary and essential for the synthesis of propargylamine.
But the transformation of propargylamines proceeded in the
presence of catalyst under atmospheric conditions, and the
reaction could be prevented when exposed to nitrogen atmo-
sphere. It could be inferred that in our investigation, the one-pot
three-component preparation of quinolines did not proceed via
propragylamines intermediate. A possible mechanism is proposed
in Scheme 7. Proton provided by montmorillonite preferentially
interacts with amino nitrogen to promote an iminium ion, and
subsequently it reacts with the triple bond of 3 activated by CuCl to
generate a vinylic intermediate. A final oxidation by O2 in air
affords the quinoline product 6. [11]
fluorinated propargylamines were prepared under solvent-free
microwave irradiation condition. Further microwave irradiation in
the presence of CuCl catalyst under atmospheric condition, the
propargylamines transformed to quinoline derivatives or decom-
posed to chalcones and anilines, depending on the substituent on
aniline ring. In the meantime, quinoline derivatives were obtained
from the one-pot three-component reaction in the presence of
montmorillonite doped with CuCl under microwave irradiation
and solvent-free conditions.
4. Experimental
4.1. General
3. Conclusion
All reactions were performed in an improved domestic Sanyo,
EM-208-EB1, microwave oven (2450 MHz, 80–750 W). TLC was
performed on precoated silica gel HSGF-254 plates (0.15–0.2 mm;
Employing fluorobenzaldehyde, aniline and phenylacetylene as
the reagents, CuCl as the catalyst, in N2 atmosphere, a series of

X.-L. Chen et al. / Journal of Fluorine Chemistry 133 (2012) 139–145
143
Huanghai), and products and starting materials were detected by
4.2.6. N-(4-Nitrophenyl)-3-amino-3-(2,5-diuorophenyl)-1-
viewing under UV light. Column chromatography was performed
on silica gel (200–300 mesh). Infrared spectra were recorded on an
AVATAR370 FT spectrophotometer (PerkinElmer, USA). NMR
spectra were determined with DRX500 MHz spectrometer (Bruker,
USA), using solutions in deuterated chloroform with tetramethyl-
silane as the internal standard for 1H, 19F and 13C nuclei,
respectively. Low resolution mass spectrum or high resolution
mass spectra were obtained on Finnigan MAT-8430 instrument
using the electron impact ionization technique (70 eV).
phenylprop-1-yne 4fc
Brown liquid, IR (KBr)
1310, 1264, 1111, 833, 755 cmÀ1 1H NMR (CDCl3, 500 MHz):
.
n
: 3374, 3081, 2925, 1598, 1493, 1445,
d
= 8.10 (d, J = 10.5 Hz, 2H), 7.45–7.41 (m, 3H), 7.40–7.33 (m, 3H),
7.13–7.01 (m, 2H), 6.71 (d, J = 10.5 Hz, 2H), 5.82 (d, J = 7 Hz, 1H),
5.20 (brs, 1H). 19F NMR (CDCl3, 470 MHz):
d
= À116.78 to À116.86
(m, 1F), À123.81 to À123.89 (m, 1F). MS (EI) m/z: 364 (M+). HRMS
(EI) m/z calcd. for C21H14F2N2O2: 364.1023; Found: 364.1020.
4.2.7. N-(4-Nitrophenyl)-3-amino-3-(3,4-diuorophenyl)-1-
4.2. Preparation of fluorinated propargylamines
phenylprop-1-yne 4gc
Yellow solid, mp 84.9–85.8 8C. IR (KBr)
1602, 1519, 1471, 1326, 1310, 1112, 834, 750 cmÀ1
(CDCl3, 500 MHz): = 8.12 (d, J = 9 Hz, 2H), 7.72–7.68 (m, 1H),
n
: 3351, 3058, 2224,
4.2.1. General procedure
.
1H NMR
Fluorobenzaldehyde 1a–1g (1 mmol), amine 2a–2c (1.2 mmol),
d
and phenylacetylene
3
(1.5 mmol) were mixed with CuCl
7.43–7.41 (m, 2H), 7.36–7.29 (m, 3H), 6.96 (td, J = 8, 2 Hz, 1H), 6.91
(td, J = 8.5, 2 Hz, 1H), 6.71 (d, J = 9 Hz, 2H), 5.80 (d, J = 6.5 Hz, 1H),
(0.3 mmol) and ground into a fine, homogeneous mixture; then
the mixture was put in a 25-mL round bottomed ask and exposed
to microwave irradiation at proper power using a microwave oven
for an appropriate time under nitrogen. After completion of the
reaction (as monitored by TLC), the reaction mixture was diluted
with ethyl acetate, and the catalyst was ltered out. After removal of
the solvent under vacuum, the crude material was purified by silica
gel column (using petroleum ether:ethyl acetate = 10:1 as elute) to
afford pure product 4.
4.94 (brs, 1H). 19F NMR (CDCl3, 470 MHz):
d
= À108.45 to À108.52
(m, 1F), À113.66 (q, 1F). MS (EI) m/z: 364 (M+). HRMS (EI) m/z calcd.
for C21H14F2N2O2: 364.1023; Found: 364.1018.
4.2.8. N-(3-Nitrophenyl)-3-amino-3-(2-uorophenyl)-1-phenylprop-
1-yne 4ab
Reddish brown liquid, IR (KBr)
1487, 1349, 1248, 756, 734, 691 cmÀ1. 1H NMR (CDCl3, 500 MHz):
= 7.76 (td, J = 7.5, 2 Hz, 1H), 7.66 (t, J = 2.5 Hz, 1H), 7.61 (d,
n: 3407, 3065, 2962, 1617, 1527,
d
4.2.2. N-(4-Nitrophenyl)-3-amino-3-(2-uorophenyl)-1-phenylprop-
J = 3 Hz, 1H), 7.48–7.43 (m, 3H), 7.34–7.28 (m, 4H), 7.22 (t,
J = 6.5 Hz, 1H), 7.14 (t, J = 8 Hz, 1H), 7.04 (dd, J = 8 Hz, 1H), 5.83 (s,
1-yne 4ac
Yellowsolid, mp 57.3–58.9 8C. IR(KBr)
1325, 1303, 1265, 1110, 754, 690 cmÀ1. 1H NMR (CDCl3, 500 MHz):
= 8.09 (d, J = 15 Hz, 2H), 7.76 (t, J = 15.5 Hz, 1H), 7.47–7.33 (m, 6H),
n: 3375, 3078, 2922, 1601,
1H), 4.65 (brs, 1H). 19F NMR (CDCl3, 470 MHz):
d
= À118.06 to
À118.11 (m, 1F). MS (EI) m/z: 346 (M+). HRMS (EI) m/z calcd. for
d
C21H15FN2O2: 346.1118; Found: 346.1114.
7.20 (t, J = 10 Hz, 1H), 7.13 (t, J = 15 Hz, 1H), 6.73 (d, J = 15 Hz, 2H),
5.81 (d, J = 13.5 Hz, 1H), 5.27 (brs, 1H). 19F NMR (CDCl3, 470 MHz):
d
4.2.9. N-(3-Nitrophenyl)-3-amino-3-(3-uorophenyl)-1-phenylprop-
= À117.99toÀ118.02(m, 1F). MS (EI)m/z: 346(M+).HRMS(EI)m/z
1-yne 4bb
calcd. for C21H15FN2O2: 346.1118; Found: 346.1122.
Reddish brown liquid, IR (KBr)
1527, 1349, 1248, 757, 735, 691 cmÀ1. 1H NMR (CDCl3, 500 MHz):
= 7.62 (d, J = 6 Hz, 2H), 7.46–7.38 (m, 5H), 7.19 (t, J = 8 Hz, 4H),
7.07 (td, J = 8 Hz, 1H), 7.02 (d, J = 7.5 Hz, 1H), 5.57 (s, 1H), 4.65 (brs,
n: 3405, 3065, 2927, 1617, 1592,
4.2.3. N-(4-Nitrophenyl)-3-amino-3-(4-uorophenyl)-1-phenylprop-
d
1-yne 4cc
Yellow solid, mp 55.3–56.6 8C. IR (KBr)
2922, 1596, 1506, 1304, 1110, 832, 758 cmÀ1
500 MHz): = 8.10 (d, J = 9 Hz, 2H), 7.62 (dd, J = 9, 5.5 Hz, 2H), 7.44
n
: 3414, 3402, 3068,
.
1H). 19F NMR (CDCl3, 470 MHz):
d
= À111.65 to À111.66 (m, 1F).
1H NMR (CDCl3,
MS (EI) m/z: 346 (M+). HRMS (EI) m/z calcd. for C21H15FN2O2:
d
346.1118; Found: 346.1116.
(dd, J = 7.5, 2 Hz, 2H), 7.35–7.29 (m, 3H), 7.11 (t, J = 8.5 Hz, 2H),
6.73 (d, J = 9 Hz, 2H), 5.59 (d, J = 5 Hz, 1H), 5.16 (brs, 1H). 19F NMR
4.2.10. N-(3-Nitrophenyl)-3-amino-3-(4-uorophenyl)-1-
(CDCl3, 470 MHz):
d
= À108.94 (s, 1F). MS (EI) m/z: 346 (M+). HRMS
phenylprop-1-yne 4cb
(EI) m/z calcd. for C21H15FN2O2: 346.1118; Found: 346.1120.
Reddish brown liquid, IR (KBr)
1527, 1349, 1226, 757, 735, 691 cmÀ1. 1H NMR (CDCl3, 500 MHz):
= 7.63 (t, J = 8.5 Hz, 4H), 7.43 (d, J = 6 Hz, 2H), 7.34–7.28 (m, 4H),
7.12 (t, J = 8.5 Hz, 2H), 7.03 (dd, J = 8, 2 Hz, 1H), 5.55 (s, 1H), 4.60
n: 3406, 3068, 2962, 1621, 1602,
4.2.4. N-(4-Nitrophenyl)-3-amino-3-(2,3-diuorophenyl)-1-
d
phenylprop-1-yne 4dc
Yellow solid, mp 86.8–87.6 8C. IR (KBr)
1602, 1526, 1488, 1325, 1303, 1267, 1112, 835, 754 cmÀ1. 1H NMR
(CDCl3, 500 MHz): = 8.10 (d, J = 9.5 Hz, 2H), 7.46 (t, J = 7.5 Hz, 1H),
n: 3362, 3056, 2924,
(brs, 1H). 19F NMR (CDCl3, 470 MHz):
d
= À113.32 to À113.38 (m,
1F); MS (EI) m/z: 346 (M+). HRMS (EI) m/z calcd. for C21H15FN2O2:
d
346.1118; Found: 346.1112.
7.42 (d, J = 6.5 Hz, 2H), 7.36–7.29 (m, 3H), 7.22–7.13 (m, 2H), 6.71
(d, J = 9.5 Hz, 2H), 5.86 (s, 1H), 5.32 (brs, 1H). 19F NMR (CDCl3,
4.3. Chemical transformation of fluorinated propargylamines
470 MHz):
(m, 1F). MS (EI) m/z: 364 (M+). HRMS (EI) m/z calcd. for
21H14F2N2O2: 364.1023; Found: 364.1024.
d
= À136.78 to À136.85 (m, 1F), À142.73 to À142.81
4.3.1. General procedure
C
Fluorinated propargylamines were mixed with montmorillon-
ite clay doped with CuCl and ground into a ne, homogeneous
mixture; then the mixture was put in a 25-mL round bottomed ask
and exposed to microwave irradiation at proper power using a
microwave oven for an appropriate time. After completion of the
reaction (as monitored by TLC), the reaction mixture was diluted
with ethyl acetate, and the catalyst and montmorillonite were
ltered out. After removal of the solvent under vacuum, the crude
material was puried by silica gel column (using petroleum
ether:ethyl acetate = 10:1 as elute) to afford chalcones 5 [12] or
quinoline derivatives 6.
4.2.5. N-(4-Nitrophenyl)-3-amino-3-(2,4-diuorophenyl)-1-
phenylprop-1-yne 4ec
Brown liquid, IR (KBr)
1348, 1315, 1111, 835, 756 cmÀ1
= 7.69–7.61 (m, 3H), 7.43 (d, J = 5 Hz, 2H), 7.33–7.28 (m, 4H), 7.12
(tt, J = 8.5, 2 Hz, 2H), 7.04–7.01 (m, 1H), 5.53 (d, J = 13 Hz, 1H), 4.57
n
: 3400, 3079, 2925, 1620, 1599, 1527,
.
1H NMR (CDCl3, 500 MHz):
d
(brs, 1H). 19F NMR (CDCl3, 470 MHz):
d
= À113.33 to À113.39 (m,
1F), À114.71 to À114.80 (m, 1F). MS (EI) m/z: 364 (M+). HRMS (EI)
m/z calcd. for C21H14F2N2O2: 364.1023; Found: 364.1027.

144
X.-L. Chen et al. / Journal of Fluorine Chemistry 133 (2012) 139–145
4.3.2. 3-(2-Fluorophenyl)-1-pnenyl-(2E)-2-propen-1-one 5a
Pale brown solid, mp 87.1–88.2 8C. IR (KBr) : 1663, 1605, 1581,
1486, 1458, 1332, 1216, 983, 771 cmÀ1. 1H NMR (CDCl3, 500 MHz):
= 8.04–8.02 (m, 2H), 7.91 (d, J = 16 Hz, 1H), 7.66–7.63 (m, 2H), 7.59
4.4. Synthesis of quinoline derivatives
n
4.4.1. General procedure
d
Fluorobenzaldehyde 1a–1g (1 mmol), amine 2a–2c (1 mmol),
and phenylacetylene 3 (2 mmol) were mixed with montmorillon-
ite doped with CuCl (0.3 mmol) and ground into a fine, homoge-
neous mixture; then the mixture was put in a 25-mL round
bottomed ask and exposed to microwave irradiation at proper
power using a microwave oven for an appropriate time. After
completion of the reaction (as monitored by TLC), the reaction
mixture was diluted with ethyl acetate, and the catalyst and
montmorillonite clay were filtered out. After removal of the
solvent under vacuum, the crude material was purified by silica gel
column (using petroleum ether:ethyl acetate = 20:1 as elute) to
afford pure product 6.
(t, J = 7.5 Hz, 1H), 7.49 (t, J = 15 Hz, 2H), 7.39–7.35 (m, 1H), 7.19 (t,
J = 7 Hz, 1H), 7.12 (t, J = 9 Hz, 1H). 19F NMR (CDCl3, 470 MHz):
d
= À113.31 to À113.36 (m, 1F). MS (EI) m/z: 226 (M+, 100).
4.3.3. 3-(3-Fluorophenyl)-1-pnenyl-(2E)-2-propen-1-one 5b
Yellowsolid, mp87.4–88.2 8C. IR(KBr) : 1665, 1605, 1582, 1487,
1458, 1331, 1215, 983, 771 cmÀ1 1H NMR (CDCl3, 500 MHz):
= 8.03–8.02(m, 2H), 7.77(d, J = 15.5 Hz,1H), 7.61(tt, J = 7.5, 1.5 Hz,
n
.
d
1H), 7.54–7.51 (m, 3H), 7.43–7.34 (m, 2H), 7.14–7.10 (m, 1H). 19F
NMR (CDCl3, 470 MHz):
125 MHz):
d
= À112.39 (s, 1F). 13C NMR (CDCl3,
d
= 190.1 (s), 164.0 (s), 162.0 (s), 143.3 (d, J = 2.5 Hz),
137.9 (s), 137.2 (d, J = 7.5 Hz), 133.0 (s), 130.5 (d, J = 7.5 Hz, 2 C),
128.6 (d, J = 20 Hz, 2 C), 124.6 (d, J = 4 Hz), 123.2 (s), 117.4 (d,
J = 21 Hz), 114.5 (d, J = 22.5 Hz). MS (EI) m/z: 226 (M+, 100).
4.4.2. 2-(2-Fluorophenyl)-6-nitro-4-phenyl-quinoline 6ac
Offwhite solid, mp 258.3–259.1 8C. IR (KBr)
1486, 1340, 1207, 1253, 759, 699 cmÀ1. 1H NMR (CDCl3, 500 MHz):
= 8.90 (d, J = 2.5 Hz, 1H), 8.51 (dd, J = 9, 2.5 Hz, 1H), 8.36 (d,
n: 3104, 1613, 1594,
4.3.4. 3-(4-Fluorophenyl)-1-pnenyl-(2E)-2-propen-1-one 5c
d
Yellowish solid, mp 85.7–87.1 8C. IR (KBr)
1485, 1459, 1330, 1216, 982, 770 cmÀ1. 1H NMR (CDCl3, 500 MHz):
= 8.03–8.01 (m, 2H), 7.79 (d, J = 16 Hz, 1H), 7.66–7.63 (m, 2H),
7.60 (t, J = 7.5 Hz, 1H), 7.53 (t, J = 15 Hz, 2H), 7.47 (d, J = 16 Hz, 1H),
7.14–7.10 (m, 2H). 19F NMR (CDCl3, 470 MHz):
n
: 1662, 1605, 1581,
J = 9 Hz, 1H), 8.20 (td, J = 8, 2 Hz, 1H), 8.02 (d, J = 2.5 Hz, 1H), 7.62–
7.57 (m, 5H), 7.53–7.51 (m, 1H), 7.37 (t, J = 7.5 Hz, 1H), 7.22 (d,
d
J = 8.5 Hz, 1H). 19F NMR (CDCl3, 470 MHz):
d
= À116.02 to À116.06
(m, 1F). MS (EI) m/z: 344 (M+). HRMS calcd. for C21H13FN2O2:
d
= À108.97 to
344.0961, Found 344.0962.
À109.03(m, 1F). HRMS (EI) m/z calcd. for C15H11FO: 226.0794;
Found 226.0791.
4.4.3. 2-(3-Fluorophenyl)-6-nitro-4-phenyl-quinoline 6bc
Faint yellow solid, mp 209.7–210.1 8C. IR (KBr)
1615, 1592, 1485, 1342, 1253, 883, 812 cmÀ1 1H NMR (CDCl3,
500 MHz): = 8.87 (d, J = 2.5 Hz, 1H), 8.51 (dd, J = 9, 2.5 Hz, 1H),
n: 3096, 3076,
4.3.5. 3-(2,3-Difluorophenyl)-1-pnenyl-(2E)-2-propen-1-one 5d
.
Yellow solid, mp 109.1–110.2 8C. IR (KBr)
1485, 1459, 1330, 1276, 973, 767 cmÀ1. 1H NMR (CDCl3, 500 MHz):
= 8.04–8.02 (m, 2H), 7.87 (d, J = 15.5 Hz, 1H), 7.67 (tt, J = 7.5,
n: 1664, 1609, 1582,
d
8.34 (d, J = 9 Hz, 1H), 8.01 (dd, J = 9, 2.5 Hz, 2H), 7.96 (s, 1H), 7.65–
d
7.51 (m, 6H), 7.25–7.21 (m, 1H). 19F NMR (CDCl3, 470 MHz):
1.5 Hz, 1H), 7.61 (t, J = 7.5 Hz, 1H), 7.56–7.51 (m, 2H), 7.42–7.39
(m, 1H), 7.24–7.19 (m, 1H), 7.16–7.14 (m, 1H). 19F NMR (CDCl3,
d
= À112.04 to À112.09 (m, 1F). MS (EI) m/z: 344 (M+). HRMS (EI)
m/z calcd. for C21H13FN2O2: 344.0961; Found: 344.0958.
470 MHz):
d
= À136.76 to À136.84 (m, 1F), À142.73 to À142.80
(m, 1F). MS (EI) m/z: 244 (M+, 100).
4.4.4. 2-(4-Fluorophenyl)-6-nitro-4-phenyl-quinoline 6cc
Yellow solid, mp 226.4–227.1 8C. IR (KBr)
1594, 1486, 1336, 1232, 836, 770 cmÀ1. 1H NMR (CDCl3, 500 MHz):
= 8.89 (d, J = 2.5 Hz, 1H), 8.50 (dd, J = 9, 2.5 Hz, 1H), 8.35 (d,
n: 3103, 3027, 1617,
4.3.6. 3-(2,4-Difluorophenyl)-1-pnenyl-(2E)-2-propen-1-one 5e
Yellow solid, mp 109.8–110.6 8C. IR (KBr)
1485, 1459, 1330, 1274, 964, 776 cmÀ1. 1H NMR (CDCl3, 500 MHz):
= 8.02 (d, J = 7 Hz, 2H), 7.85 (d, J = 15.5 Hz, 1H), 7.66–7.58 (m, 3H),
n: 1662, 1607, 1589,
d
J = 9 Hz, 1H), 8.27 (dd, J = 9, 5.5 Hz, 2H), 7.99 (d, J = 2.5 Hz, 1H),
d
7.67–7.56 (m, 6H), 7.13–7.10 (m, 1H). 19F NMR (CDCl3, 470 MHz):
7.53–7.50 (m, 2H), 6.97–6.89 (m, 2H). 19F NMR (CDCl3, 470 MHz):
d
C
= À110.07 (s, 1F). MS (EI) m/z: 344 (M+). HRMS (EI) m/z calcd. for
d
= À105.56 to À105.62 (m, 1F), À108.74 to À108.81 (m, 1F). 13C
21H13FN2O2: 344.0961; Found: 344.0960.
NMR (CDCl3, 125 MHz):
d = 190.3 (s), 165.1 (d, J = 12.5 Hz), 163.1
(d, J = 12.5 Hz), 161.1 (d, J = 12.5 Hz), 137.9 (s), 136.5 (d, J = 7.5 Hz),
133.1 (s), 131.1 (s, 2C), 130.9 (t, J = 5 Hz, 2C), 124.2 (s), 119.7 (s),
112.3 (s), 105.0 (s); MS (EI) m/z: 244 (M+, 100).
4.4.5. 2-(2,4-Difluorophenyl)-6-nitro-4-phenyl-quinoline 6ec
Offwhite solid, mp 232.3–233.1 8C. IR (KBr) : 3101, 1613, 1591,
1484, 1338, 1264, 846, 697 cmÀ1 1H NMR (CDCl3, 500 MHz):
= 8.86 (d, J = 2.5 Hz, 1H), 8.50 (d, J = 9 Hz, 1H), 8.35 (d, J = 9 Hz,
1H), 8.27 (d, J = 9 Hz, 1H), 7.94 (s, 1H), 7.65–7.54 (m, 5H), 7.27–7.23
n
.
d
4.3.7. 3-(2,5-Difluorophenyl)-1-pnenyl-(2E)-2-propen-1-one 5f
Yellow solid, mp 110.1–111.3 8C. IR (KBr)
1458, 1333, 1269, 974, 726 cmÀ1 1H NMR (CDCl3, 500 MHz):
= 8.04–7.98 (m, 2H), 7.85 (d, J = 15.5 Hz, 1H), 7.63–7.59 (m, 2H),
7.54–7.51 (m, 2H), 7.36–7.32 (m, 1H), 7.13–7.06 (m, 2H). 19F NMR
n
: 1662, 1605, 1487,
(m, 2H). 19F NMR (CDCl3, 470 MHz):
d
= À105.53 to À105.60 (m,
.
1F); À108.72 to À108.78 (m, 1F). MS (EI) m/z: 362 (M+). HRMS (EI)
m/z calcd. for C21H12F2N2O2: 362.0867; Found: 362.0865.
d
(CDCl3, 470 MHz):
d
= À118.17 to À118.25 (m, 1F), À119.45 to
4.4.6. 2-(2,5-Difluorophenyl)-6-nitro-4-phenyl-quinoline 6fc
À119.57 (m, 1F). 13C NMR (CDCl3, 125 MHz):
d
= 190.0 (s), 159.8
Yellow solid, mp 232.5–233.2 8C. IR (KBr)
1591, 1493, 1336, 1256, 816, 695 cmÀ1. 1H NMR (CDCl3, 500 MHz):
= 8.91 (d, J = 2.5 Hz, 1H), 8.53 (dd, J = 9.5, 2.5 Hz, 1H), 8.37 (d,
n: 3103, 3081, 1618,
(s), 158.8 (s), 157.8 (s), 137.8 (s), 136.1 (s), 133.2 (s), 128.8 (d,
J = 17.5 Hz, 2 C), 125.5 (s, 2C), 125.4 (s), 118.3 (s), 117.5 (s), 115.2
(s). MS (EI) m/z: 244 (M+, 100).
d
J = 9.5 Hz, 1H), 8.05 (d, J = 6.5 Hz, 1H), 8.02–7.96 (m, 1H), 7.64–7.56
(m, 5H), 7.23–7.18 (m, 2H). 19F NMR (CDCl3, 470 MHz):
4.3.8. 3-(3,4-Difluorophenyl)-1-pnenyl-(2E)-2-propen-1-one 5g
d
= À117.72 (s, 1F); À121.60 (m, 1F). MS (EI) m/z: 362 (M+). HRMS
Yellow solid, mp 114.5–115.3 8C. IR (KBr)
1455, 1332, 1276, 987, 775 cmÀ1 1H NMR (CDCl3, 500 MHz):
= 8.02–8.01 (m, 2H), 7.71 (d, J = 15.5 Hz, 1H), 7.63–7.59 (m, 1H),
7.55–7.50 (m, 2H), 7.48–7.43 (m, 2H), 7.38–7.36 (m, 1H), 7.24–7.19
n: 1661, 1606, 1514,
(EI) m/z calcd. for C21H12F2N2O2: 362.0867; Found: 362.0868.
.
d
4.4.7. 2-(3-Fluorophenyl)-7-nitro-4-phenyl-quinoline 6bb
Yellow solid, mp 209.9–210.7 8C. IR (KBr)
1523, 1356, 1183, 828, 784, 703 cmÀ1. 1H NMR (CDCl3, 500 MHz):
= 8.49 (dd, J = 8.5, 1 Hz, 1H), 8.00–7.98 (m, 2H), 7.92 (s, 1H), 7.91
n: 3067, 1613, 1586,
(m, 1H). 19F NMR (CDCl3, 470 MHz):
1F), À137.25 to À137.34 (m, 1F). MS (EI) m/z: 244 (M+, 100).
d
= À135.68 to À137.25 (m,
d

X.-L. Chen et al. / Journal of Fluorine Chemistry 133 (2012) 139–145
145
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(d, J = 7.5 Hz, 1H), 7.81 (t, J = 8.5 Hz, 1H), 7.53–7.48(m, 4H), 7.42–
7.41(m, 2H), 7.22 (t, J = 7.5 Hz, 1H). 19F NMR (CDCl3, 470 MHz):
d
= À112.06 to À112.11(m, 1F). MS (EI) m/z: 344 (M+). HRMS (EI)
m/z calcd. for C21H13FN2O2: 344.0961; Found: 344.0965.
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Offwhite solid, mp 226.1–227.1 8C. IR (KBr)
1593, 1512, 1348, 1230, 839, 697 cmÀ1. 1H NMR (CDCl3, 500 MHz):
= 9.13 (d, J = 2.5 Hz, 1H), 8.27–8.22 (m, 2H), 8.06 (d, J = 9 Hz, 1H),
n: 3080, 1661, 1603,
d
8.01 (d, J = 7 Hz, 1H), 7.95 (s, 1H), 7.61–7.59 (m, 3H), 7.56–7.55 (m,
1H), 7.25 (t, J = 3.5 Hz, 2H), 7.12 (t, J = 8.5 Hz, 1H). 19F NMR (CDCl3,
470 MHz):
d
= À110.52 (s, 1F). MS (EI) m/z: 344 (M+).
Acknowledgements
This work was supported by the National Science Foundation of
China (no. 20972092).
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