A facile and expeditious microwave-assisted synthesis of 4-aryl-2-ferrocenyl-quinoline derivatives via multi-component reaction

Article abstract of DOI:10.1016/j.jorganchem.2008.10.007

An efficient and rapid route for the synthesis of 4-aryl-2-ferrocenyl-quinoline derivatives through microwave-assisted multi-component reaction of acetylferrocene with aromatic aldehyde and dimedone in the presence of ammonium acetate using DMF as reactio

Full text of DOI:10.1016/j.jorganchem.2008.10.007

Journal of Organometallic Chemistry 694 (2009) 91–96
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
A facile and expeditious microwave-assisted synthesis of
4-aryl-2-ferrocenyl-quinoline derivatives via multi-component reaction
*
Shu-Jiang Tu , Shu Yan, Xu-Dong Cao, Shan-Shan Wu, Xiao-Hong Zhang, Wen-Juan Hao, Zheng-Guo Han,
Feng Shi
College of Chemistry and Chemical Engineering, Xuzhou Normal University, Key Laboratory of Biotechnology for medicinal Plant, Xuzhou, Jiangsu 221116, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
An efficient and rapid route for the synthesis of 4-aryl-2-ferrocenyl-quinoline derivatives through micro-
wave-assisted multi-component reaction of acetylferrocene with aromatic aldehyde and dimedone in the
presence of ammonium acetate using DMF as reaction media at 100 °C is described. This novel procedure
lends itself well to combinatorial methods, providing the target heteropolymetallic compounds in excel-
lent yield without further purification.
Received 4 September 2008
Received in revised form 5 October 2008
Accepted 7 October 2008
Available online 14 October 2008
Ó 2008 Elsevier B.V. All rights reserved.
Keywords:
Ferrocene
Heteropolymetallic compound
4-Aryl-2-ferrocenyl-quinoline
Multi-component reaction
1. Introduction
cally active and exist in the structures of various antimalarial
and antitumor agents [27–29]. Consequently, integration of a ferr-
Since the report of ferrocene by Kealy and Pauson [1], an impor-
tant area of organometallic chemistry is focused on ferrocene and
its derivatives. Ferrocene derivatives containing heterocyclic sys-
tems have attracted special attention in recent years [2–7] because
of their organic and inorganic properties, as well as for their appli-
cations in various areas including components of molecular wires
[8], anion sensors [9] and potential organic ferromagnets [10].
Compared with the classical heterocyclic compounds, incorpora-
tion of a ferrocene fragment into heterocycles often obtained unex-
pected biological activity [11]. Furthermore, ferrocene has been
studied extensively as it is thought to be responsible for a variety
of biological stability and non-toxicity rendering such drugs com-
patible with other treatment [12–14]. In the light of current stud-
ies, the combination of ferrocene units with heterocyclic molecules
offers a desired way to endow novel functional molecules [15–17].
The quinoline moiety is one of the significant core structures
among the most extensively natural and unnatural heterocyclic
compounds [18–21] with remarkable medicinal activities [22]. In
particular, quinolines have played a unique role in the design
and synthesis of novel biologically active compounds serving as
antiinflammatory, antiasthmatic, antituberculosis, antibacterial,
antihypertensive, antitumor, and, most notably, antimalarial
agents [18,23–26]. Moreover, ferrocenyl substitutes are biologi-
ocenyl moiety into quinoline derivatives may increase their biolog-
ical activities or create new medicinal properties [30–33].
Although much work has been directed toward the synthetic
manipulation of quinoline derivatives, the synthesis of ferroce-
nyl-substituted quinolines [34–37], especially 2-ferrocenylquino-
lin-5(1H,4H,6H)-ones, has seldom been reported. As a result, the
synthesis of ferrocenyl heterocycles is a key desiderated issue in
organometallic chemistry.
With the aim to develop efficient synthetic processes, reduce
laborious multi-steps and minimize byproducts, as well as in
continuation of recent interest in the organoferrocene chemistry
[38–41], here we describe a practical, inexpensive, and rapid
microwave-promoted (MW) method for the preparation of 2-
ferrocenyl-quinoline derivatives 5 via multi-component reactions
of acetylferrocene 1, aromatic aldehyde 2, dimedone 3 and ammo-
nium acetate 4 in DMF (Scheme 1).
2. Results and discussion
To choose the most appropriate solvent, the MW-assisted reac-
tion (Scheme 2) of acetylferrocene (1, 1.0 mmol), 4-chlorobenzal-
dehyde (2a, 1.0 mmol), dimedone (3, 1.0 mmol) and ammonium
acetate (4, 2.5 mmol) was examined using glacial acetic acid
(HOAc), glycol, N,N-dimethylformamide (DMF), water as the sol-
vent (2.0 mL) and solvent-free at 80 °C, respectively. All the reac-
tions were carried out at the maximum power of 200 W. As
* Corresponding author. Tel./fax: +86 516 83500065.
E-mail address: laotu2001@263.net (S.-J. Tu).
0022-328X/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2008.10.007

92
S.-J. Tu et al. / Journal of Organometallic Chemistry 694 (2009) 91–96
Table 3
Ar
O
O
Synthesis of compound 5 under microwave irradiation.
O
O
ArCHO
Entry
Product
Ar
Time (min)
Yield (%)
Mp (°C)
2
DMF
MW
+
+
Fe
N
H
1
2
3
4
5
6
7
8
9
5a
5b
5c
5d
5e
5f
5g
5h
5i
4-ClC6H4
4-BrC6H4
4-MeC6H4
4-MeOC6H4
3,4-(MeO)2C6H3
3,4,5-(MeO)3C6H2
4-Me2NC6H4
Thiophen-2-yl
3,4-(OCH2O)C6H3
10
9
92
93
90
91
78
79
75
86
82
238–240
241–244
221–223
213–215
192–195
197–199
198–201
206–208
228–231
Fe
NH4OAc
sealed tube
100oC
11
12
13
15
12
10
12
4
1
5
3
Scheme 1.
Cl
shown in Table 1, we could see the reaction in DMF gave the best
results (Table 1, entry 3). So DMF was chosen as the reaction
solvent.
Cl
O
O
O
O
DMF
MW
+ NH4OAc
+
+
Fe
To further optimize reaction conditions, the same reaction was
performed in DMF and 200 W at temperatures ranging from 70 to
130 °C, with an increment of 10 °C each time. The yield of product
5a was increased and the reaction time was shortened as the tem-
perature was raised from 70 °C to 100 °C (Table 2, entries 1–4).
However, no significant increase in the yield of product 5a was ob-
served as the reaction temperature was raised from 110 °C to
130 °C (Table 2, entries 5–7). Therefore, 100 °C was chosen as the
reaction temperature for all further reactions.
N
H
CHO
Fe
3
1
2a
4
5a
Scheme 2.
Table 1
Solvent optimization for the synthesis of 5a under microwave irradiation.
Under the optimal conditions [DMF, 100 °C, 200 W (maximum
power)], reactions of different aromatic aldehydes were performed
and afforded 2-ferrocenylquinolin-5(1H,4H,6H)-ones with good
yields. As shown in Table 3, at the beginning, we made a search
for the aldehyde substrate scope, acetylferrocene and dimedone
were used as model substrates (Table 3, entries 1–9), and the re-
sults indicated that aromatic aldehydes bearing either electron-
donating or electron-withdrawing functional groups such as
chloro, bromo, methyl, or methoxy were able to affect the synthe-
sis of compounds 5. We have also observed delicate electronic ef-
fects: that is, aryl aldehydes with electron-withdrawing groups
(Table 3, entries 1 and 2) reacted rapidly, while the substitution
of electron-rich groups (Table 3, entries 3–7 and 9) on the benzene
ring decreased the reactivity, requiring longer reaction times.
Moreover, the heterocyclic aldehydes such as thiophene-2-carbal-
dehyde (Table 3, entry 8) still displayed a high reactivity under this
standard condition. It is worth noting that this conclusion is signif-
icant since there is no literature precedent for the synthesis of 2-
ferrocenylquinolin-5(1H,4H,6H)-ones.
Entry
Solvent
Temperature (°C)
Time (min)
Yield (%)
1
2
3
4
5
HOAc
Glycol
DMF
Water
None
80
80
80
80
80
15
10
15
8
Trace
36
82
49
27
7
Table 2
Temperature optimization for the synthesis of 5a under microwave irradiation.
Entry
Temperature (°C)
Time (min)
Yield (%)
1
2
3
4
5
6
7
70
80
90
100
110
120
130
20
15
12
10
8
41
82
83
92
78
66
60
7
5
The formation of 5 is expected to proceed via initial condensa-
tion of aldehydes with dimedone to afford 2-arylidene-5,5-dimeth-
O
O
NH2
NH
O
O
O
Ar
NH3
Ar
3
Fe
Fe
Fe
H
O
2
1
9
10
Ar
O
Ar
O
-H2O
NH2
O
N
H
Fe
Fe
5
11
Scheme 3.

S.-J. Tu et al. / Journal of Organometallic Chemistry 694 (2009) 91–96
93
complexity. Central to our approach was to develop a simple meth-
od, using readily available starting materials and simple
experimental procedures, for the rapid synthesis of diverse polyhy-
droquinoline derivatives.
In a further study, thiophene-2-carbaldehyde was employed in
the synthesis of 7 (Scheme 5). The reactions proceeded to unex-
pected products 8 [47] when arones with electron-rich groups (Ta-
ble 4, entry 18) were as precursors whereas the substitution of
electron-withdrawing groups (Table 4, entries 12 and 17) on the
arone ring generated desired products 7 in high yields (Scheme
5). The results are summarized in Table 4.
ArCHO
Ar
O
O
2
NH4OAc
+
+
Ar'
MW
sealed tube
N
H
Ar'
O
O
6
3
7
Scheme 4.
ylcyclohexane-1,3-dione 9, which further undergoes in situ Mi-
chael addition with 1-ferrocenylethenamine 10, obtained by treat-
ing acetylferrocene with ammonia from ammonium acetate, to
yield intermediate 11, which is then cyclized to afford the products
5 (Scheme 3).
3. Conclusion
In summary, we demonstrated a rapid and direct method that
offered a simple and efficient route for the one-pot, four-compo-
nent synthesis of poly-substituted quinolines (4-aryl-2-ferroce-
nyl-quinolines and 2,4-diarylpolyhydroquinolines) in good to
excellent yields. Particularly valuable features of this method in-
cluded operational simplicity, increased safety for small-scale
high-speed synthesis, and broader substrate scope.
In order to further expand the scope of the present method, the
replacement of acetylferrocene with various arones including 6a–e
was examined (Scheme 4). In all these cases, the reactions pro-
ceeded smoothly to give the corresponding 2,4-diarylpolyhydro-
quinolines 7 in good yields (Table 4).
Although a good many of methods for the synthesis of the 2,4-
diarylpolyhydroquinolines have been reported [42–46], all of the
present methods still have limitations of inaccessibility of precur-
sors, multi-step processes, narrow substrate scope and operational
4. Experimental
4.1. General information and the microwave reactor
TM
All reactions were performed in a monomodal Emrys Creator
Table 4
Synthesis of compound 7 under microwave irradiationa.
from Personal Chemistry, Uppsala, Sweden. Melting points were
determined in open capillaries and are uncorrected. IR spectra
were recorded on a FT-IR-tensor 27 spectrometer in KBr. 1H NMR
spectra were measured on a DPX 400 MHz spectrometer using
TMS as an internal standard and DMSO-d6 as solvent. Elemental
analysis was determined by using a Perkin–Elmer 240c elemental
analysis instrument.
Entry Productb Ar
6
Ar0
Time Yieldc Mp
(min) (%)
(°C)
1
2
3
4
5
6
7
8
7a
7b
7c
7d
7e
7f
7g
7h
7i
4-ClC6H4
Ph
4-MeC6H4
6a Ph
6a Ph
6a Ph
10
13
11
12
87
83
85
90
80
91
92
90
93
81
95
90
82
80
90
75
83
70
221–223
223–224
227–229
231–232
237–239
218–221
270–271
248–251
259–261
274–276
280–281
241–244
265–266
270–272
256–257
279–281
235–237
>300
4-OH-3-O2NC6H3 6a Ph
4-ClC6H4
4-MeOC6H4
4-ClC6H4
Ph
4-MeC6H4
4-O2NC6H4
6b 4-MeOC6H4 11
6b 4-MeOC6H4 13
6c 4-O2NC6H4
6c 4-O2NC6H4 11
6c 4-O2NC6H4
6c 4-O2NC6H4 10
4.2. General procedure for the synthesis of 4-aryl-2-ferrocenyl-
quinoline derivatives 5 under microwave irradiation
8
9
9
10
11
12
13
14
15
16
17
18
7j
All microwave-assisted reactions were performed in a mono-
7k
7l
4-OH-3-O2NC6H3 6c 4-O2NC6H4
9
8
12
13
14
9
TM
modal Emrys Creator from Personal Chemistry, Uppsala, Sweden.
Thiophen-2-yl
4-BrC6H4
6c 4-O2NC6H4
6d 4-BrC6H4
6d 4-BrC6H4
6d 4-BrC6H4
6d 4-BrC6H4
6d 4-BrC6H4
6a Ph
TM
Typically, in
a 10 mL Emrys reaction vial, acetylferrocenyl
7m
7n
7o
7p
7q
8
Ph
(1 mmol), aromatic aldehyde (1 mmol), dimedone (1 mmol) and
ammonium acetate (2.5 mmol) in DMF (2 mL) were mixed and
then capped. The mixture was irradiated by microwave at 200 W
and 100 °C for a given time. The automatic mode stirring helped
the mixing and uniform heating of the reactants. Upon completion,
monitored by TLC, the reaction mixture was cooled to room tem-
perature and washed with 2 mL 95% EtOH, filtered to give the
crude products, which were further purified by recrystallization
from 95% EtOH. The reaction time and the yields are listed in Table
3. The analytical data of new products are as following:
4-MeC6H4
4-O2NC6H4
Thiophen-2-yl
Thiophen-2-yl
9
8
6b 4-MeOC6H4
a
b
c
The power of MWI was 200 W at 100 °C.
All the reactions are carried out with NH4OAC in the sealed tube.
Isolated yields.
4-(4-Chlorophenyl)-7,8-dihydro-7,7-dimethyl-2-ferrocenylquino-
lin-5(1H,4H,6H)-one (5a): yellow solid; IR (KBr):
2958, 2865, 1668 (C@O), 1587, 1491, 1307, 1251, 1131, 1085, 819,
596 cmꢀ1 1H NMR (400 MHz, DMSO-d6, 25 °C): d = 7.99 (s, 1H,
m 3300 (NH), 3098,
Ar
O
Ar
O
O
H
O
;
2
O
NH4OAc
NH), 7.29 (s, 2H, ArH), 7.24 (s, 2H, ArH), 5.13 (s, 1H, CH), 4.66 (d,
J = 12.8 Hz, 2H, ferroceneyl), 4.40 (s, 1H, CH), 4.26 (s, 2H, ferroce-
neyl), 4.12 (s, 5H, ferroceneyl), 2.17 (d, J = 16.4 Hz, 1H, CH), 1.99
(d, J = 16.8 Hz, 1H, CH), 1.04 (s, 3H, CH3), 0.95 (s, 3H, CH3); 13C
NMR (100 MHz, DMSO-d6, 25 °C): d = 193.7, 152.2, 147.5, 132.8,
130.0, 129.1, 127.8, 105.8, 101.6, 80.0, 69.1, 68.6, 68.4, 65.2, 65.0,
50.2, 36.4, 32.0, 28.9, 26.9. Anal. Calc. for C27H26ClFeNO: C, 68.73;
H, 5.55; N, 2.97. Found: C, 68.86; H, 5.45; N, 2.93%.
+
N
H
8
Ar'
O
O
6
3
Ar
Ar = thiophen-2-yl
Ar'= C6H4,4-MeOC6H4
N
H
7
Ar'
4-(4-Bromophenyl)-7,8-dihydro-7,7-dimethyl-2-ferrocenylquino-
lin-5(1H,4H,6H)-one (5b): yellow solid; IR (KBr):
m 3301 (NH), 3090,
Scheme 5.

94
S.-J. Tu et al. / Journal of Organometallic Chemistry 694 (2009) 91–96
2957, 2864, 1668 (C@O), 1588, 1492, 1307, 1252, 1130, 1082, 817,
592 cmꢀ1 1H NMR (400 MHz, DMSO-d6, 25 °C): d = 8.00 (s, 1H,
4-(4-(Dimethylamino)phenyl)-7,8-dihydro-7,7-dimethyl-2-ferroce-
nylquinolin-5(1H,4H,6H)-one (5g): yellow solid; IR (KBr): 3300
(NH), 3089, 2949, 2886, 1664 (C@O), 1580, 1494, 1380, 1306,
1253, 1133, 1080, 951, 815, 654, 594 cmꢀ1 1H NMR (400 MHz,
;
m
NH), 7.43 (d, J = 8.0 Hz, 2H, ArH), 7.18 (d, J = 8.4 Hz, 2H, ArH),
5.13 (d, J = 4.8 Hz, 1H, CH), 4.66 (d, J = 13.2 Hz, 2H, ferroceneyl),
4.39 (d, J = 5.2 Hz, 1H, CH), 4.26 (s, 2H, ferroceneyl), 4.13 (s, 5H,
ferroceneyl), 2.52 (s, 2H, CH2), 2.17 (d, J = 16.4 Hz, 1H, CH), 1.99
(d, J = 16.8 Hz, 1H, CH), 1.04 (s, 3H, CH3), 0.95 (s, 3H, CH3); 13C
NMR (100 MHz, DMSO-d6, 25 °C): d = 193.7, 152.2, 147.9, 132.8,
130.8, 129.5, 118.4, 105.7, 101.6, 80.0, 69.1, 68.6, 68.4, 65.2, 65.0,
50.3, 36.5, 32.0, 28.9, 27.0. Anal. Calc. for C27H26BrFeNO: C,
62.82; H, 5.08; N, 2.71. Found: C, 62.97; H, 5.12; N, 2.69%.
;
DMSO-d6, 25 °C): d = 7.85 (s, 1H, NH), 7.03 (d, J = 8.4 Hz, 2H, ArH),
6.60 (d, J = 8.8 Hz, 2H, ArH), 5.10 (d, J = 4.8 Hz, 1H, CH), 4.67 (s
1H, ferroceneyl), 4.62 (s, 1H, ferroceneyl), 4.26 (s, 1H, CH), 4.24
(s, 2H, ferroceneyl), 4.13 (s, 5H, ferroceneyl), 2.80 (s, 6H, 2CH3),
2.15 (d, J = 16.0 Hz, 1H, CH), 1.96 (d, J = 16.0 Hz, 1H, CH), 1.04 (s,
3H, CH3), 0.96 (s, 3H, CH3); 13C NMR (100 MHz, DMSO-d6, 25 °C):
d = 193.6, 151.4, 148.7, 136.9, 131.7, 127.9, 112.3, 106.7, 102.7,
80.5, 69.1, 68.4, 68.3, 65.1, 64.9, 50.4, 40.4, 35.7, 31.9, 29.1, 26.9.
Anal. Calc. for C29H32FeN2O: C, 72.50; H, 6.71; N, 5.83. Found: C,
72.41; H, 6.68; N, 5.80%.
7,8-Dihydro-7,7-dimethyl-2-ferrocenyl-4-p-tolylquinolin-5(1H,4H,
6H)-one (5c): yellow solid; IR (KBr): m 3300 (NH), 3081, 2958, 2866,
1669 (C@O), 1581, 1491, 1358, 1252, 1105, 999, 819, 591 cmꢀ1; 1H
NMR (400 MHz, DMSO-d6, 25 °C): d = 7.92 (s, 1H, NH), 7.11 (s, 2H,
ArH), 7.04 (s, 2H, ArH), 5.13 (s, 1H, CH), 4.68 (s, 1H, ferroceneyl),
4.63 (s, 1H, ferroceneyl), 4.34 (s, 1H, CH), 4.25 (s, 2H, ferroceneyl),
4.13 (s, 5H, ferroceneyl), 2.22 (s, 3H, CH3), 2.16 (d, J = 16.0 Hz, 1H,
CH), 1.98 (d, J = 16.0 Hz, 1H, CH), 1.05 (s, 3H, CH3), 0.96 (s, 3H, CH3);
13C NMR (100 MHz, DMSO-d6, 25 °C): d = 193.6, 151.8, 145.7, 134.3,
132.2, 128.4, 127.2, 106.3, 102.4, 80.3, 69.1, 68.5, 68.4, 65.1, 65.0,
50.3, 36.5, 31.9, 29.0, 26.9, 20.5. Anal. Calc. for C28H29FeNO: C,
74.50; H, 6.48; N, 3.10. Found: C, 74.38; H, 6.51; N, 2.98%.
7,8-Dihydro-7,7-dimethyl-2-ferrocenyl-4-(thiophen-2-yl)quinolin-
5(1H,4H,6H)-one (5h): yellow solid; IR (KBr):
2959, 2868, 1661 (C@O), 1590, 1486, 1379, 1256, 1134, 1082,
816, 696 cmꢀ1 1H NMR (400 MHz, DMSO-d6, 25 °C): d = 8.08 (s,
m 3324 (NH), 3093,
;
1H, NH), 7.23 (d, J = 4.8 Hz, 1H, thienyl-H), 6.86 (t, J = 4.0 Hz, 1H,
thienyl-H), 6.80 (s, 1H, thienyl-H), 5.24 (d, J = 5.2 Hz, 1H, CH),
4.73 (d, J = 6.8 Hz, 1H, CH), 4.68 (d, J = 13.6 Hz, 2H, ferroceneyl),
4.27 (s, 2H, ferroceneyl), 4.16 (s, 5H, ferroceneyl), 2.20 (d,
J = 16.0 Hz, 1H, CH), 2.03 (d, J = 16.0 Hz, 1H, CH), 1.05 (s, 3H,
CH3), 0.98 (s, 3H, CH3); 13C NMR (100 MHz, DMSO-d6, 25 °C):
d = 193.6, 153.0, 151.7, 133.3, 126.3, 123.5, 122.3, 106.1, 100.8,
80.0, 69.1, 68.6, 68.5, 65.3, 65.1, 50.3, 31.9, 31.4, 29.1, 26.7. Anal.
Calc. for C25H25FeNOS: C, 67.72; H, 5.68; N, 3.16; S, 7.23. Found:
C, 67.85; H, 5.72; N, 3.13; S, 7.20%.
7,8-Dihydro-4-(4-methoxyphenyl)-7,7-dimethyl-2-ferrocenylquin-
olin-5(1H,4H,6H)-one (5d): yellow solid; IR (KBr):
3095, 2958, 2865, 1666 (C@O), 1583, 1491, 1379, 1253, 1105,
1034, 821, 591 cmꢀ1 1H NMR (400 MHz, DMSO-d6, 25 °C):
m 3302 (NH),
;
d = 7.91 (s, 1H, NH), 7.13 (d, J = 7.2 Hz, 2H, ArH), 6.79 (d,
J = 7.6 Hz, 2H, ArH), 5.12 (s, 1H, CH), 4.67 (s, 1H, ferroceneyl),
4.63 (s, 1H, ferroceneyl), 4.33 (d, J = 4.0 Hz, 2H, CH), 4.25 (s, 2H,
ferroceneyl), 4.13 (s, 5H, ferroceneyl), 2.15 (d, J = 15.6 Hz, 1H,
CH), 1.97 (d, J = 16.0 Hz, 1H, CH), 1.04 (s, 3H, CH3), 0.95 (s, 3H,
CH3); 13C NMR (100 MHz, DMSO-d6, 25 °C): d = 193.6, 157.2,
151.7, 140.8, 132.1, 128.2, 113.3, 106.4, 102.4, 80.4, 69.1, 68.5,
68.3, 65.1, 64.9, 54.9, 50.4, 35.9, 32.0, 29.0, 26.9. Anal. Calc. for
C28H29FeNO2: C, 71.95; H, 6.25; N, 3.00. Found: C, 72.07; H, 6.31;
N, 2.95%.
4-(Benzo[d][1,3]dioxol-6-yl)-7,8-dihydro-7,7-dimethyl-2-ferroce-
nylquinolin-5(1H,4H,6H)-one (5i): yellow solid; IR (KBr):
(NH), 3079, 2952, 2889, 1665 (C@O), 1599, 1483, 1387, 1294,
1138, 1038, 925, 809, 592 cmꢀ1 1H NMR (400 MHz, DMSO-d6,
m 3358
;
25 °C): d = 7.97 (s, 1H, NH), 6.80–6.72 (m, 3H, ArH), 5.92 (s 2H,
CH2), 5.15 (s 1H, CH), 4.68 (s, 2H, ferroceneyl), 4.67 (s, 1H, CH),
4.27 (s, 2H, ferroceneyl), 4.14 (s, 5H, ferroceneyl), 2.20–1.98 (m,
2H, CH2), 1.08–0.98 (m, 6H, 2CH3). Anal. Calc. for C28H27FeNO3: C,
69.86; H, 5.65; N, 2.91. Found: C, 70.01; H, 5.70; N, 2.88%.
7,8-Dihydro-4-(3,4-dimethoxyphenyl)-7,7-dimethyl-2-ferrocenyl-
quinolin-5(1H,4H,6H)-one (5e): yellow solid; IR (KBr):
3094, 2953, 2833, 1625 (C@O), 1587, 1492, 1378, 1260, 1126, 1030,
806, 592 cmꢀ1 1H NMR (400 MHz, DMSO-d6, 25 °C): d = 7.91 (s,
m
3297 (NH),
4.3. General procedure for the synthesis of 2,4-
diarylpolyhydroquinolines 7 under microwave irradiation
;
1H, NH), 6.82–6.80 (m, 2H, ArH), 6.73–6.69 (m, 1H, ArH), 5.13 (d,
J = 5.2 Hz, 1H, CH), 4.67 (s, 1H, ferroceneyl), 4.61 (s, 1H, ferroce-
neyl), 4.32 (d, J = 5.2 Hz, 1H, CH), 4.25 (s, 2H, ferroceneyl), 4.12
(s, 5H, ferroceneyl), 3.69–3.62 (m, 6H, 2OCH3), 2.52 (s, 1H, CH),
2.17 (d, J = 16.4 Hz, 1H, CH), 2.08 (s, 1H, CH), 1.98 (d, J = 16.0 Hz,
1H, CH), 1.05 (s, 3H, CH3), 0.99 (s, 3H, CH3); 13C NMR (100 MHz,
DMSO-d6, 25 °C): d = 193.8, 151.9, 148.4, 146.9, 141.5, 132.0,
119.2, 111.6, 111.5, 106.2, 102.5, 80.3, 69.1, 68.5, 68.4, 65.1, 65.0,
55.5, 55.3, 50.3, 36.4, 31.9, 29.2, 26.7. Anal. Calc. for C29H31FeNO3:
C, 70.03; H, 6.28; N, 2.82. Found: C, 70.14; H, 6.23; N,
2.80%.
In a 10-mL reaction vial, arones (1 mmol), aromatic aldehyde
(1 mmol), dimedone (1 mmol) were mixed in the present of
ammonium acetate (2.5 mmol) and then the vial was capped.
The mixture was irradiated for a given time at maximum power
of 200 W and 100 °C. When the reaction was completed (moni-
tored by TLC), the subsequent workup was the performed as for
the preparation of 5 under microwave irradiation.
4-(4-Chlorophenyl)-7,8-dihydro-7,7-dimethyl-2-phenylquinolin-
5(1H,4H,6H)-one (7a): yellow crystal; IR (KBr):
2952, 2865, 1661 (C@O), 1583, 1494, 1393, 1278, 1122, 1087, 822,
767, 697, 594 cmꢀ1 1H NMR (400 MHz, DMSO-d6, 25 °C): d = 8.64
m 3231 (NH), 3057,
;
7,8-Dihydro-4-(3,4,5-trimethoxyphenyl)-7,7-dimethyl-2-ferrocenyl-
(s, 1H, NH), 7.50–7.47 (m, 2H, ArH), 7.41–7.35 (m, 3H, ArH), 7.29
(d, J = 8.4 Hz, 2H, ArH), 7.23 (d, J = 8.4 Hz, 2H, ArH), 5.18 (dd,
J1 = 5.2 Hz, J2 = 1.6 Hz, 1H, CH), 4.57 (d, J = 5.6 Hz, 1H, CH), 2.46
(d, J = 5.2 Hz, 2H, CH2), 2.17 (d, J = 16.0 Hz, 1H, CH), 2.00 (d,
J = 16.0 Hz, 1H, CH), 1.03 (s, 3H, CH3), 0.94 (s, 3H, CH3). Anal. Calc.
for C23H22ClNO: C, 75.92; H, 6.09; N, 3.85. Found: C, 76.02; H, 6.05;
N, 3.83%.
quinolin-5(1H,4H,6H)-one (5f): yellow solid; IR (KBr):
3094, 2956, 2833, 1682 (C@O), 1586, 1496, 1379, 1305, 1247,
1127, 1033, 1006, 815, 669, 591 cmꢀ1 1H NMR (400 MHz,
m 3308 (NH),
;
DMSO-d6, 25 °C): d = 7.93 (s, 1H, NH), 6.50 (s, 2H, ArH), 5.14 (d,
J = 4.4 Hz, 1H, CH), 4.67 (s, 1H, ferroceneyl), 4.62 (s, 1H, ferroce-
neyl), 4.34 (d, J = 5.2 Hz, 1H, CH), 4.25 (s, 2H, ferroceneyl), 4.11
(s, 5H, ferroceneyl), 3.71 (s, 6H, 2OCH3), 3.59 (s, 3H, OCH3), 2.55
(s, 2H, CH2), 2.20 (d, J = 16.0 Hz, 1H, CH), 2.01 (d, J = 16.0 Hz, 1H,
CH), 1.07 (s, 3H, CH3), 1.05 (s, 3H, CH3); 13C NMR (100 MHz,
DMSO-d6, 25 °C): d = 193.8, 152.5, 152.2, 144.6, 135.5, 132.0,
105.7, 104.5, 102.5, 80.2, 69.1, 68.6, 68.4, 65.2, 65.0, 59.9, 55.6,
50.3, 37.3, 31.9, 29.3, 26.6. Anal. Calc. for C30H33FeNO4: C, 68.32;
H, 6.31; N, 2.66. Found: C, 68.43; H, 6.38; N, 2.68%.
7,8-Dihydro-7,7-dimethyl-2,4-diphenylquinolin-5(1H,4H,6H)-one
(7b): yellow crystal; IR (KBr):
(C@O), 1590, 1491, 1328, 1240, 1153, 1055, 846, 766, 698, 577
cmꢀ1 1H NMR (400 MHz, DMSO-d6, 25 °C): d = 8.58 (s, 1H, NH),
m 3284 (NH), 3075, 2957, 2867, 1656
;
7.49–7.47 (m, 2H, ArH), 7.40–7.34 (m, 3H, ArH), 7.26–7.21 (m,
4H, ArH), 7.12–7.07 (m, 1H, ArH), 5.21 (dd, J1 = 6.0 Hz, J2 = 2.0 Hz,
1H, CH), 4.56 (d, J = 5.2 Hz, 1H, CH), 2.47 (d, J = 3.6 Hz, 2H, CH2),

S.-J. Tu et al. / Journal of Organometallic Chemistry 694 (2009) 91–96
95
2.17 (d, J = 16.0 Hz, 1H, CH), 1.99 (d, J = 16.0 Hz, 1H, CH), 1.03 (s,
3H, CH3), 0.95 (s, 3H, CH3). Anal. Calc. for C23H23NO: C, 83.85; H,
7.04; N, 4.25. Found: C, 83.95; H, 6.99; N, 4.23%.
1H, CH), 2.49 (s, 2H, CH2), 2.18 (d, J = 16.0 Hz, 1H, CH), 2.02 (d,
J = 16.4 Hz, 1H, CH), 1.04 (s, 3H, CH3), 0.97 (s, 3H, CH3). Anal. Calc.
for C23H22N2O3: C, 73.78; H, 5.92; N, 7.48. Found: C, 73.65; H, 5.96;
N, 7.51%.
7,8-Dihydro-7,7-dimethyl-2-phenyl-4-p-tolylquinolin-5(1H,4H,6H)-
one (7c): yellow crystal; IR (KBr):
1661 (C@O), 1583, 1491, 1385, 1278, 1121, 1060, 810, 769, 697,
594 cmꢀ1 1H NMR (400 MHz, DMSO-d6, 25 °C): d = 8.58 (s, 1H,
NH), 7.48–7.46 (m, 2H, ArH), 7.40–7.34 (m, 3H, ArH), 7.10 (d,
J = 8.0 Hz, 2H, ArH), 7.03 (d, J = 8.0 Hz, 2H, ArH), 5.18 (dd,
J1 = 5.2 Hz, J2 = 1.6 Hz, 1H, CH), 4.51 (d, J = 5.2 Hz, 1H, CH), 2.46
(d, J = 6.4 Hz, 2H, CH2), 2.22 (s, 3H, CH3), 2.16 (d, J = 16.0 Hz, 1H,
CH), 1.98 (d, J = 16.0 Hz, 1H, CH), 1.03 (s, 3H, CH3), 0.94 (s, 3H,
CH3). Anal. Calc. for C24H25NO: C, 83.93; H, 7.34; N, 4.08. Found:
C, 84.04; H, 7.37; N, 4.06%.
m
3232 (NH), 3053, 2951, 2865,
7,8-Dihydro-7,7-dimethyl-2-(4-nitrophenyl)-4-p-tolylquinolin-5
(1H,4H,6H)-one (7i): yellow crystal; IR (KBr):
2964, 2886, 1635 (C@O), 1593, 1489, 1338, 1242, 1125, 1056,
850, 752, 690, 580 cmꢀ1 1H NMR (400 MHz, DMSO-d6, 25 °C):
m 3260 (NH), 3074,
;
;
d = 8.74 (s, 1H, NH), 8.23 (d, J = 9.2 Hz, 2H, ArH), 7.76 (d,
J = 8.8 Hz, 2H, ArH), 7.11 (d, J = 8.0 Hz, 2H, ArH), 7.04 (d,
J = 8.0 Hz, 2H, ArH), 5.46 (dd, J1 = 5.6 Hz, J2 = 1.6 Hz, 1H, CH), 4.55
(d, J = 5.6 Hz, 1H, CH), 2.47 (s, 2H, CH2), 2.22 (s, 3H, CH3), 2.18 (d,
J = 16.0 Hz, 1H, CH), 2.00 (d, J = 16.0 Hz, 1H, CH), 1.04 (s, 3H,
CH3), 0.96 (s, 3H, CH3). Anal. Calc. for C24H24N2O3: C, 74.21; H,
6.23; N, 7.21. Found: C, 74.30; H, 6.27; N, 7.18%.
7,8-Dihydro-4-(4-hydroxy-3-nitrophenyl)-7,7-dimethyl-2-phenyl-
quinolin-5(1H,4H,6H)-one (7d): yellow solid; IR (KBr):
2948, 2886, 1659 (C@O), 1590, 1483, 1327, 1232, 1056, 828, 759,
685, 571 cmꢀ1 1H NMR (400 MHz, DMSO-d6, 25 °C): d = 10.67 (s,
1H, OH), 8.71 (s, 1H, NH), 7.68 (s, 1H, ArH), 7.51–7.36 (m, 6H,
ArH), 7.05 (d, J = 8.4 Hz, 2H, ArH), 5.22 (dd, J1 = 5.2 Hz, J2 = 1.6 Hz,
1H, CH), 4.59 (d, J = 5.2 Hz, 1H, CH), 2.47 (d, J = 8.0 Hz, 2H, CH2),
2.19 (d, J = 16.0 Hz, 1H, CH), 2.00 (d, J = 16.0 Hz, 1H, CH), 1.03 (s,
3H, CH3), 0.94 (s, 3H, CH3). Anal. Calc. for C23H22N2O4: C, 70.75;
H, 5.68; N, 7.17. Found: C, 70.88; H, 5.71; N, 7.15%.
m
3369 (NH),
7,8-Dihydro-7,7-dimethyl-2,4-bis(4-nitrophenyl)quinolin-5(1H,
4H,6H)-one (7j): yellow solid; IR (KBr):
2867, 1657 (C@O), 1592, 1487, 1339, 1244, 1108, 1057, 852, 752,
695, 586 cmꢀ1 1H NMR (400 MHz, DMSO-d6, 25 °C): d = 8.93 (s,
m 3345 (NH), 3077, 2951,
;
;
1H, NH), 8.24 (d, J = 8.8 Hz, 2H, ArH), 8.15 (d, J = 8.0 Hz, 2H, ArH),
7.78 (d, J = 9.2 Hz, 2H, ArH), 7.50 (d, J = 8.4 Hz, 2H, ArH), 5.47 (dd,
J1 = 5.2 Hz, J2 = 1.6 Hz, 1H, CH), 4.78 (d, J = 5.2 Hz, 1H, CH), 2.49
(s, 2H, CH2), 2.20 (d, J = 16.0 Hz, 1H, CH), 2.03 (d, J = 16.0 Hz, 1H,
CH), 1.05 (s, 3H, CH3), 0.96 (s, 3H, CH3). Anal. Calc. for
C23H21N3O5: C, 65.86; H, 5.05; N, 10.02. Found: C, 65.74; H, 5.03;
N, 9.99%.
4-(4-Chlorophenyl)-7,8-dihydro-2-(4-methoxyphenyl)-7,7-dimeth-
ylquinolin-5(1H,4H,6H)-one (7e): yellow crystal; IR (KBr):
(NH), 3199, 3073, 2997, 2866, 1662 (C@O), 1609, 1588, 1499,
1389, 1237, 1185, 1057, 822, 625, 551 cmꢀ1 1H NMR (400MHz,
m 3237
7,8-Dihydro-4-(4-hydroxy-3-nitrophenyl)-7,7-dimethyl-2-(4-nitro-
;
phenyl)quinolin-5(1H,4H,6H)-one (7k): yellow solid; IR (KBr):
3287 (NH), 3063, 2965, 2868, 1625 (C@O), 1589, 1499, 1337,
1244, 1155, 1060, 851, 755, 691, 590 cmꢀ1 1H NMR (400MHz,
m
DMSO-d6, 25 °C): d = 8.57 (s, 1H, NH), 7.41 (d, J = 8.8 Hz, 2H,
ArH), 7.29 (d, J = 8.4 Hz, 2H, ArH), 7.22 (d, J = 8.4 Hz, 2H, ArH),
6.94 (d, J = 8.8 Hz, 2H, ArH), 5.08 (dd, J1 = 5.2 Hz, J2 = 1.6 Hz, 1H,
CH), 4.55 (d, J = 5.6 Hz, 1H, CH), 3.76 (s, 3H, OCH3), 2.46 (d,
J = 5.2 Hz, 2H, CH2), 2.16 (d, J = 16.0 Hz, 1H, CH), 1.99 (d,
J = 16.0 Hz, 1H, CH), 1.02 (s, 3H, CH3), 0.93 (s, 3H, CH3). Anal. Calc.
for C24H24ClNO2: C, 73.18; H, 6.14; N, 3.56. Found: C, 73.03; H,
6.17; N, 3.52%.
;
DMSO-d6, 25 °C): d = 10.72 (s, 1H, OH), 8.89 (s, 1H, NH), 8.25 (d,
J = 9.2 Hz, 2H, ArH), 7.79 (d, J = 9.2 Hz, 2H, ArH), 7.69 (s, 1H, ArH),
7.45 (dd, J1 = 8.4 Hz, J2 = 2.0 Hz, 1H, ArH), 7.06 (d, J = 8.4 Hz, 1H,
ArH), 5.49 (dd, J1 = 5.6 Hz, J2 = 1.6 Hz, 1H, CH), 4.63 (d, J = 5.6 Hz,
1H, CH), 2.49 (s, 2H, CH2), 2.20 (d, J = 16.0 Hz, 1H, CH), 2.03 (d,
J = 16.0 Hz, 1H, CH), 1.05 (s, 3H, CH3), 0.96 (s, 3H, CH3). Anal. Calc.
for C23H21N3O6: C, 63.44; H, 4.86; N, 9.65. Found: C, 63.36; H, 4.89;
N, 9.70%.
7,8-Dihydro-2,4-bis(4-methoxyphenyl)-7,7-dimethylquinolin-5
(1H,4H,6H)-one (7f): yellow crystal; IR (KBr):
3071, 2951, 2866, 1660 (C@O), 1586, 1491, 1391, 1237, 1184,
1033, 830, 762, 623, 534 cmꢀ1 1H NMR (400 MHz, DMSO-d6,
m 3239 (NH), 3267,
7,8-Dihydro-7,7-dimethyl-2-(4-nitrophenyl)-4-(thiophen-2-yl)qui-
;
nolin-5(1H,4H,6H)-one (7l): yellow crystal; IR (KBr):
3077, 2955, 2883, 1650 (C@O), 1594, 1490, 1339, 1242, 1123,
1057, 851, 696, 592 cmꢀ1 1H NMR (400 MHz, DMSO-d6, 25 °C):
m 3280 (NH),
25 °C): d = 8.47 (s, 1H, NH), 7.41 (d, J = 8.8 Hz, 2H, ArH), 7.11 (d,
J = 8.4 Hz, 2H, ArH), 6.93 (d, J = 9.2 Hz, 2H, ArH), 6.79 (d,
J = 8.4 Hz, 2H, ArH), 5.08 (dd, J1 = 5.6 Hz, J2 = 1.6 Hz, 1H, CH), 4.47
(d, J = 5.2 Hz, 1H, CH), 3.76 (s, 3H, OCH3), 3.68 (s, 3H, OCH3), 2.44
(d, J = 6.0 Hz, 2H, CH2), 2.15 (d, J = 16.0 Hz, 1H, CH), 1.97 (d,
J = 16.0 Hz, 1H, CH), 1.02 (s, 3H, CH3), 0.93 (s, 3H, CH3). Anal. Calc.
for C25H27NO3: C, 77.09; H, 6.99; N, 3.60. Found: C, 77.17; H, 7.04;
N, 3.57%.
;
d = 8.93 (s, 1H, NH), 8.26 (d, J = 8.8 Hz, 2H, ArH), 7.80 (d,
J = 8.8 Hz, 2H, ArH), 7.25 (d, J = 5.2 Hz, 1H, thienyl-H), 6.88 (dd,
J1 = 5.2 Hz, J2 = 3.6 Hz, 1H, thienyl-H), 6.82 (d, J = 3.2 Hz, 1H, thie-
nyl-H), 5.57 (dd, J1 = 5.6 Hz, J2 = 1.6 Hz, 1H, CH), 4.92 (d,
J = 5.6 Hz, 1H, CH), 2.49 (s, 1H, CH), 2.42 (d, J = 16.8 Hz, 1H, CH),
2.22 (d, J = 16.0 Hz, 1H, CH), 2.06 (d, J = 16.0 Hz, 1H, CH), 1.05 (s,
3H, CH3), 0.98 (s, 3H, CH3). Anal. Calc. for C21H20N2O3S: C, 66.29;
H, 5.30; N, 7.36; S, 8.43. Found: C, 66.35; H, 5.28; N, 7.41; S, 8.39%.
2,4-Bis(4-bromophenyl)-7,8-dihydro-7,7-dimethylquinolin-5(1H,
4-(4-Chlorophenyl)-7,8-dihydro-7,7-dimethyl-2-(4-nitrophenyl)-
quinolin-5(1H,4H,6H)-one (7g): yellow solid; IR (KBr):
3110, 3077, 2948, 2866, 1659 (C@O), 1588, 1488, 1347, 1247,
1123, 1013, 850, 752, 696, 560 cmꢀ1 1H NMR (400 MHz, DMSO-
m 3330 (NH),
;
4H,6H)-one (7m): white solid; IR (KBr):
2866, 1652 (C@O), 1609, 1586, 1485, 1385, 1238, 1126, 1069,
1008, 818, 586 cmꢀ1 1H NMR (400 MHz, DMSO-d6, 25 °C):
m 3331 (NH), 3072, 2952,
d6, 25 °C): d = 8.82 (s, 1H, NH), 8.24 (d, J = 8.8 Hz, 2H, ArH), 7.78
(d, J = 9.2 Hz, 2H, ArH), 7.31 (d, J = 8.4 Hz, 2H, ArH), 7.24 (d,
J = 8.4 Hz, 2H, ArH), 5.47 (dd, J1 = 5.6 Hz, J2 = 1.6 Hz, 1H, CH), 4.62
(d, J = 5.6 Hz, 1H, CH), 2.49 (d, J = 2.8 Hz, 2H, CH2), 2.18 (d,
J = 16.0 Hz, 1H, CH), 2.02 (d, J = 16.0 Hz, 1H, CH), 1.04 (s, 3H,
CH3), 0.95 (s, 3H, CH3). Anal. Calc. for C23H21ClN2O3: C, 67.56; H,
5.18; N, 6.85. Found: C, 67.64; H, 5.21; N, 6.86%.
;
d = 8.68 (s, 1H, NH), 7.58 (d, J = 8.4 Hz, 2H, ArH), 7.45–7.42 (m,
4H, ArH), 7.17 (d, J = 8.4 Hz, 2H, ArH), 5.23 (dd, J1 = 5.6 Hz,
J2 = 1.6 Hz, 1H, CH), 4.55 (d, J = 5.2 Hz, 1H, CH), 2.46 (d, J = 7.6 Hz,
2H, CH2), 2.17 (d, J = 16.0 Hz, 1H, CH), 1.99 (d, J = 16.0 Hz, 1H,
CH), 1.03 (s, 3H, CH3), 0.94 (s, 3H, CH3). Anal. Calc. for C23H21Br2NO:
C, 56.70; H, 4.34; N, 2.87. Found: C, 56.83; H, 4.36; N, 2.90%.
2-(4-Bromophenyl)-7,8-dihydro-7,7-dimethyl-4-phenylquinolin-5
7,8-Dihydro-7,7-dimethyl-2-(4-nitrophenyl)-4-phenylquinolin-5
(1H,4H,6H)-one (7h): yellow crystal; IR (KBr):
2941, 2887, 1644 (C@O), 1590, 1503, 1392, 1241, 1126, 1056,
850, 752, 699, 585 cmꢀ1 1H NMR (400 MHz, DMSO-d6, 25 °C):
m 3250 (NH), 3073,
(1H,4H,6H)-one (7n): white solid; IR (KBr):
2959, 2866, 1665 (C@O), 1586, 1497, 1326, 1239, 1122, 886, 769,
695, 592 cmꢀ1 1H NMR (400 MHz, DMSO-d6, 25 °C): d = 8.62 (s,
m 3228 (NH), 3065,
;
d = 8.76 (s, 1H, NH), 8.23 (d, J = 9.2 Hz, 2H, ArH), 7.77 (d,
J = 9.2 Hz, 2H, ArH), 7.27–7.22 (m, 4H, ArH), 7.13–7.09 (m, 1H,
ArH), 5.49 (dd, J1 = 5.6 Hz, J2 = 1.6 Hz, 1H, CH), 4.60 (d, J = 5.6 Hz,
;
1H, NH), 7.57 (d, J = 8.4 Hz, 2H, ArH), 7.44 (d, J = 8.8 Hz, 2H, ArH),
7.26–7.20 (m, 4H, ArH), 7.12–7.08 (m, 1H, ArH), 5.26 (dd, J1 = 5.6

96
S.-J. Tu et al. / Journal of Organometallic Chemistry 694 (2009) 91–96
Hz, J2 = 1.6 Hz, 1H, CH), 4.55 (d, J = 5.2 Hz, 1H, CH), 2.47 (d,
J = 5.6 Hz, 2H, CH2), 2.17 (d, J = 16.0 Hz, 1H, CH), 2.00 (d,
J = 16.0 Hz, 1H, CH), 1.03 (s, 3H, CH3), 0.95 (s, 3H, CH3). Anal. Calc.
for C23H22BrNO: C, 67.65; H, 5.43; N, 3.43. Found: C, 67.72; H, 5.41;
N, 3.46%.
References
[1] T.J. Kealy, P.L. Pauson, Nature 168 (1951) 1039.
[2] C. López, S. Pérez, X. Solans, M. Font-Bardía, A. Roig, E. Molins, P.W.N.M. van
Leeuwen, G.P.F. vand Strijdonck, Organometallics 26 (2007) 571.
[3] S. Pérez, C. López, A. Caubet, X. Solans, M. Font-Bardía, A. Roig, E. Molins,
Organometallics 25 (2006) 596.
[4] A. Moyano, M. Rosol, R.M. Moreno, C. López, M.A. Maestro, Angew. Chem., Int.
Ed. 44 (2005) 1865.
[5] R. Gómez Arrayas, J. Adrio, J.C. Carretero, Angew. Chem., Int. Ed. 45 (2006)
7674.
2-(4-Bromophenyl)-7,8-dihydro-7,7-dimethyl-4-p-tolylquinolin-5
(1H,4H,6H)-one (7o): white solid; IR (KBr):
2969, 2865, 1650 (C@O), 1602, 1579, 1486, 1387, 1238, 1127,
1008, 803, 640, 560 cmꢀ1 1H NMR (400 MHz, DMSO-d6, 25 °C):
m 3320 (NH), 3080,
;
[6] C.E. Anderson, Y. Donde, D. Yariv, J. Christopher, L.E. Overman, J. Org. Chem. 70
(2005) 648.
[7] P.N. Kelly, A. Pretre, S. Devoy, I. O’Rielly, R. Devery, A. Goel, J.F. Gallagher, A.J.
d = 8.59 (s, 1H, NH), 7.57 (d, J = 8.8 Hz, 2H, ArH), 7.43 (d,
J = 8.4 Hz, 2H, ArH), 7.09 (d, J = 8.0 Hz, 2H, ArH), 7.03 (d,
J = 8.0 Hz, 2H, ArH), 5.23 (dd, J1 = 5.6 Hz, J2 = 1.6 Hz, 1H, CH), 4.50
(d, J = 5.2 Hz, 1H, CH), 2.45 (d, J = 7.6 Hz, 2H, CH2), 2.22 (s, 3H,
CH3), 2.16 (d, J = 16.0 Hz, 1H, CH), 1.98 (d, J = 16.0 Hz, 1H, CH),
1.03 (s, 3H, CH3), 0.94 (s, 3H, CH3). Anal. Calc. for C24H24BrNO:
C, 67.65; H, 5.43; N, 3.43. Found: C, 67.78; H, 5.48; N,
3.45%.
ˆ
Lough, P.T.M. Kenny, J. Organomet. Chem. 692 (2007) 1327.
[8] J.M. Lehn, Angew. Chem., Int. Ed. Engl. 29 (1990) 1304–1319.
[9] P.D. Beer, C.A.P. Dickson, N. Fletcher, A.J. Goulden, A. Grieve, J. Hodacora, T.
Wear, J. Chem, Soc. Chem. Commun. 10 (1993) 828–830.
[10] J.S. Miller, A.J. Epstein, Angew. Chem., Int. Ed. Engl. 33 (1994) 385–415.
[11] R.P. Hanzlik, P. Soine, W.N. Soine, J. Med. Chem. 22 (1979) 424–428.
[12] C. Biot, L. Delhaes, L.A. Maciejewaski, M. Mortuaire, D. Camus, D. Dive, J.S.
Brocard, Eur. J. Med. Chem. 35 (2000) 707.
2-(4-Bromophenyl)-7,8-dihydro-7,7-dimethyl-4-(4-nitrophenyl)-
[13] C. Biot, G. Glorian, L.A. Maciejewaski, J.S. Brocard, J. Med. Chem. 40 (1997)
3715–3718.
[14] C. Biot, L. Delhaes, M. N’Diaye, L.A. Maciejewaski, D. Camus, D. Dive, J.S.
Brocard, Bioorg. Med. Chem. 7 (1999) 2843.
[15] B. Cottineau, P. Toto, C. Marot, A. Pipaud, J. Chenault, Bioorg. Med. Chem. Lett.
12 (2002) 2105.
[16] H. Yu, L. Shao, J. Fang, J. Organomet. Chem. 692 (2007) 991.
[17] M. Zora, M. Görmen, J. Organomet. Chem. 692 (2007) 5026.
[18] B. Gabriele, R. Mancuso, G. Salerno, G. Ruffolo, P. Plastina, J. Org. Chem. 72
(2007) 6873.
[19] X. Zhang, M.A. Campo, T. Yao, R.C. Larock, Org. Lett. 7 (2005) 763.
[20] Y. Kuninobu, Y. Inoue, K. Takai, Chem. Lett. 36 (2007) 1422.
[21] M.J. Sandelier, P. DeShong, Org. Lett. 9 (2007) 3209.
[22] J.P. Michael, Nat. Prod. Rep. 24 (2007) 223.
[23] M.P. Maguire, K.R. Sheets, K. McVety, A.P. Spada, A. Zilberstein, J. Med. Chem.
37 (1994) 2129.
[24] R.D. Larsen, E.G. Corley, A.O. King, J.D. Carroll, P. Davis, T.R. Verhoeven, P.J.
Reider, M. Labelle, J.Y. Gauthier, Y.B. Xiang, R.J. Zamboni, J. Org. Chem. 61
(1996) 3398.
[25] D. Doube, M. Blouin, C. Brideau, C. Chan, S. Desmarais, D. Eithier, J.P.
Falgueyret, R.W. Friesen, M. Girrard, Y. Girard, J. Guay, P. Tagari, R.N. Young,
Bioorg. Med. Chem. Lett. 8 (1998) 1255.
quinolin-5(1H,4H,6H)-one (7p): yellow solid; IR (KBr):
3078, 2953, 2869, 1654 (C@O), 1591, 1485, 1340, 1239, 1127, 1006,
829, 756, 543 cmꢀ1 1H NMR (400 MHz, DMSO-d6, 25 °C): d = 8.79
m 3354 (NH),
;
(s, 1H, NH), 8.15 (d, J = 8.8 Hz, 2H, ArH), 7.59 (d, J = 8.4 Hz, 2H,
ArH), 7.49–7.44 (m, 4H, ArH), 5.24 (dd, J1 = 5.2 Hz, J2 = 1.6 Hz, 1H,
CH), 4.73 (d, J = 5.2 Hz, 1H, CH), 2.48 (s, 1H, CH), 2.19 (d,
J = 16.0 Hz, 1H, CH), 2.08 (s, 1H, CH), 2.01 (d, J = 16.0 Hz, 1H, CH),
1.04 (s, 3H, CH3), 0.95 (s, 3H, CH3). Anal. Calc. for C23H21BrN2O3:
C, 60.94; H, 4.67; N, 6.18. Found: C, 61.04; H, 4.71; N, 6.21%.
2-(4-Bromophenyl)-7,8-dihydro-7,7-dimethyl-4-(thiophen-2-yl)-
quinolin-5(1H,4H,6H)-one (7q): white solid; IR (KBr):
3076, 2959, 2870, 1653 (C@O), 1594, 1488, 1386, 1239, 1008,
807, 699, 516 cmꢀ1 1H NMR (400 MHz, DMSO-d6, 25 °C): d = 8.79
m 3275 (NH),
;
(s, 1H, NH), 7.61 (d, J = 8.8 Hz, 2H, ArH), 7.47 (d, J = 8.4 Hz, 2H,
ArH), 7.23 (dd, J1 = 5.2 Hz, J2 = 1.2 Hz,, 1H, thienyl-H), 6.87 (dd,
J1 = 4.8 Hz, J2 = 3.2 Hz, 1H, thienyl-H), 6.80 (d, J = 3.6 Hz, 1H, thie-
nyl-H), 5.35 (dd, J1 = 5.6 Hz, J2 = 1.6 Hz, 1H, CH), 4.87 (d,
J = 5.6 Hz, 1H, CH), 2.46 (s, 1H, CH), 2.38 (d, J = 17.2 Hz, 1H, CH),
2.21 (d, J = 16.0 Hz, 1H, CH), 2.04 (d, J = 16.0 Hz, 1H, CH), 1.03 (s,
3H, CH3), 0.96 (s, 3H, CH3). Anal. Calc. for C21H20BrNOS: C, 60.87;
H, 4.87; N, 3.38; S, 7.74. Found: C, 60.79; H, 4.91; N, 3.42; S,
7.78%.
[26] G. Roma, M.D. Braccio, G. Grossi, F. Mattioli, M. Ghia, Eur. J. Med. Chem. 35
(2000) 1021.
[27] T. Itoh, S. Shirakami, N. Ishida, Y. Yamashita, T. Yoshida, H.-S. Kim, Y. Wataya,
Bioorg. Med. Chem. Lett. 10 (2000) 1657–1659.
[28] P. Köpf-Maier, H. Kö pf, E. Neuse, Angew. Chem., Int. Ed. Engl. 23 (1984) 456–457.
[29] G.J. Atwell, B.C. Baguley, W.A. Denny, J. Med. Chem. 32 (1989) 396.
[30] S. Top, B. Dauer, J. Vaissermann, G. Jaouen, J. Organomet. Chem. 541 (1997)
355–361.
[31] S. Top, A. Vessieres, C. Cabestaing, I. Laios, G. Leclerq, C. Provot, G. Jaouen, J.
Organomet. Chem. 637–639 (2001) 500.
[32] S. Top, A. Vessieres, G. Leclercq, J. Quivy, J. Tang, J. Vaissermann, M. Huche, G.
Jaouen, Chem. Eur. J. 9 (2003) 5223.
[33] E. Hillard, A. Vessieres, L. Thouin, G. Jaouen, C. Amatore, Angew. Chem., Int. Ed.
45 (2006) 285.
[34] F. Gelin, R.P. Thummel, J. Org. Chem. 57 (1992) 3780.
[35] R. Martinez, D.J. Ramon, M. Yus, Tetrahedron 62 (2006) 8988.
[36] O.N. Chupakhin, I.A. Utepova, I.S. Kovalev, V.L. Rusinov, Z.A. Starikova, Eur. J.
Org. Chem. 5 (2007) 857–862.
[37] Z. Metin, V. Özlem, J. Organomet. Chem. 693 (2008) 2159.
[38] Q. Zhuang, R. Jia, S. Tu, J. Zhang, B. Jiang, Y. Zhang, C. Yao, J. Heterocycl. Chem.
44 (2007) 895.
[39] J.B. Heilmann, E.A. Hillard, M.A. Plamont, P. Pigeon, M. Bolte, G. Jaouen, A.
Vessières, J. Organomet. Chem. 693 (2008) 1716.
3,4,6,7-Tetrahydro-3,3,6,6-tetramethyl-9-(thiophen-2-yl)acridine-
1,8(2H,5H,9H,10H)-dione (8a): yellow crystal; IR (KBr):
(NH), 3065, 2956, 2931, 2872, 1638 (C@O), 1633 (C@O), 1609,
1482, 1371, 1219, 1141, 1003, 980, 850, 716, 691, 558 cmꢀ1 1H
m 3276
;
NMR (400 MHz, DMSO-d6, 25 °C): d = 9.43 (s, 1H, NH), 7.13 (dd,
J1 = 4.8 Hz, J2 = 1.2 Hz, 1H, thienyl-H), 6.80–6.77 (m, 1H, thienyl-
H), 6.65 (d, J = 3.2 Hz, 1H, thienyl-H), 5.14 (s, 1H, CH), 2.44 (d,
J = 17.2 Hz, 2H, CH2), 2.31 (d, J = 17.2 Hz, 2H, CH2), 2.21 (d,
J = 16.0 Hz, 2H, CH2), 2.07 (d, J = 16.0 Hz, 2H, CH2), 1.02 (s, 6H,
2CH3), 0.93 (s, 6H, 2CH3).
[40] Y.S. Xie, X.H. Pan, B.X. Zhao, J.T. Liu, D.S. Shin, J.H. Zhang, L.W. Zheng, J. Zhao,
J.Y. Miao, J. Organomet. Chem. 693 (2008) 1367.
Acknowledgements
[41] R. Pratap, V.J. Ram, Tetrahedron Lett. 49 (2008) 394.
[42] D.G. Powers, D.S. Casebier, D. Fokas, W.J. Ryan, J.R. Troth, D.L. Coffen,
Tetrahedron 54 (1998) 4085.
This work was supported by the National Natural Science
Foundation of China (No. 20672090), Natural Science Foundation
of the Jiangsu Province (No. BK2006033), Six Kind of Professional
Elite Foundation of the Jiangsu Province (No. 06-A-039), and
Graduate Foundation of Xuzhou Normal University (No.
08YLB028).
[43] T.S. Jin, Y. Yin, L.B. Liu, T.S. Li, Arkivoc (2006) 28.
[44] X.S. Wang, D.Q. Shi, S.J. Tu, Synth. Commun. 32 (2002) 3449.
[45] X. Hu, X. Zhang, X. Fan, G. Qu, Y. Li, J. Chem. Res. (2005) 697.
[46] W.Y. Chen, J. Lu, J.R. Jin, Lett. Org. Chem. 3 (2006) 317.
[47] S.J. Tu, Z.S. Lu, D.Q. Shi, C.S. Yao, Y. Gao, C. Guo, Synth. Commun. 32 (2002) 2181.