Microwave promoted catalyst-free benzylic C-H functionalization of methyl quinoline and Michael addition to beta-nitro styrene

Article abstract of DOI:10.1016/j.tetlet.2013.01.007

A catalyst-free aqueous mediated C-H activation of methyl quinolines and addition to various beta-nitro styrenes were executed under Microwave irradiation. Catalyst-free, additive free, simple workup, clean reaction conditions, easy isolation and environmentally benign medium are the best features of the present protocol.

Full text of DOI:10.1016/j.tetlet.2013.01.007

Accepted Manuscript
Microwave promoted catalyst-free benzylic C-H functionalization of methyl
quinoline and Michael addition to beta-nitro styrene
N. Nageswara Rao, H.M. Meshram
PII:
S0040-4039(13)00031-2
DOI:
http://dx.doi.org/10.1016/j.tetlet.2013.01.007
TETL 42383
Reference:
To appear in:
Tetrahedron Letters
Received Date:
Revised Date:
Accepted Date:
13 December 2012
1 January 2013
3 January 2013
Please cite this article as: Nageswara Rao, N., Meshram, H.M., Microwave promoted catalyst-free benzylic C-H
functionalization of methyl quinoline and Michael addition to beta-nitro styrene, Tetrahedron Letters (2013), doi:
http://dx.doi.org/10.1016/j.tetlet.2013.01.007
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Microwave promoted catalyst-free benzylic
C-H functionalization of methyl quinoline and
Michael addition to beta-nitro styrene
N. Nageswara Rao, H. M. Meshram*
Ar
H2O
MW, 102 0C
Ar
NO2
+
NO2
N
N
R
R
3
1
2
R
= H, NO2
Ar = 3,4-Dimethoxyphenyl, 3 ,4-Methylenedioxyphenyl, 4-Methoxyphenyl, 4-Tolyl, Phenyl,
4-Chlorophenyl, 4-BromoPhenyl, 2-Furanyl, 2-Thienyl, 2-Napthyl, 2-Methoxyphenyl

Tetrahedron Letters
1
Microwave promoted catalyst-free benzylic C-H functionalization of methyl
quinoline and Michael addition to beta-nitro styrene
N. Nageswara Rao, H. M. Meshram,*
Medicinal Chemistry and Pharmacology Division,
CSIR-Indian Institute of Chemical Technology,
Hyderabad–500 007, India.
Abstract— A catalyst-free aqueous mediated C-H activation of methyl quinolines and addition to various beta-nitro styrenes
was executed under Microwave irradiation. Catalyst-free, additive free, simple workup, clean reaction conditions, easy
isolation and environmentally benign medium are the best features of the present protocol.
Keywords: Catalyst-free conditions, Microwave, Methyl quinoline, Nitro styrene and Water.
C-H functionalization by forming a carbon-carbon bond
attracts considerable attention in modern organic synthesis.
The advantage of the C-H functionalization lies in the
simplicity of the total process. In respect of this, many
excellent results have been reported on C- H activation, the
majority of the catalytic processes reported were applicable to
only sp2 C-H bonds.1 The functionalization of sp3 C-H bonds
is still a particularly difficult challenge owing to the strength
of sp3 C-H bonds. In context to this, in the last few years,
some promising catalytic systems for the selective
functionalization of sp3 C-H bonds have been developed.
Recently, sp3 C-H bond activation of 2-alkyl substituted aza-
arene catalyzed 2 by transition metals, Lewis acid or Bronsted
acid have been reported. However, many of these methods are
associated with various drawbacks such as use of metal
catalysts, tedious experimental procedures, unsatisfactory
yields, long reaction times, and usage of expensive and
moisture sensitive catalysts. In continuation of our work, the
of toxic by-products, but often faces significant limitations
with respect to dissolution and scope. Water above its boiling
point acts as a pseudo organic solvent5a and also is a polar
solvent, consequently microwaves interact well with water
and have been successfully engaged as a catalyst for various
organic reactions.6 Thus, development of an efficient and
convenient synthetic methodology employing water medium
is the subject of interest in the recent days.
Table 1: Reaction condition screeninga
T (0C)
Yieldb (%)
Entry
Solvent
Catalyst (mol %)
Iodine
development of catalyst-free and additive free carbon-carbon
3
n.r
n.r
n.r
n.r
70
70
90
90
1
2
THF
THF
bond formation reactions,
we became interested in
developing an efficient route to C-H bond activation of
methyl quinolines. Herein, we wish to report the MW assisted
catalyst-free sp3 C-H functionalization of 2-methyl quinolines
and Michael addition to nitro styrenes affording alkyl aza-
arenes in good yields (Scheme 1). The aza-arenes products
can exhibit potent biological, chemical and pharmaceutical
properties. 4
CH3CN
CH3CN
3
4
Iodine
Iodine
n.r
20
90
100
100
80
5
6
1,2-DCE
DMF
DMSO
H2O
30
50
70
80
7
8
Ar
H2O
MW, 102 0
Ar
NO2
NO2
+
C
N
N
R
R
3
H2O
100
102
1
2
9
R = H, NO2
H2O
10
Ar = 3,4 Dimethoxyphenyl, 3 ,4-Methylenedioxyphenyl, 4-Methoxyphenyl, 4-Tolyl, Phenyl,
4-Chlorophenyl, 4-BromoPhenyl, 2-Furanyl, 2-Thienyl, 2-Napthyl, 2-Methoxyphenyl
aReaction conditions: methyl quinoline (1.5 mmol), nitro styrene
(1 mmol) and H2O (3 ml) under ambient conditions for 25 min. in
MW. bIsolated yield
Scheme1: Activation of methyl quinoline sp3 C-H bond and
addition to nitro styrenes
Initially, the reaction of methyl quinoline (1a) with β-nitro
styrene (2e) was chosen as a model reaction and several
solvents such as THF, acetonitrile, 1, 2-DCE, DMF, DMSO
and H2O were screened (Table 1). The optimization included
selecting the most suitable solvents and proportions of
MW energy has tremendous benefits in organic synthesis
and represents now a reliable tool for organic chemists.5
Water is the ideal solvent because of its abundance, and lack

2
Tetrahedron Letters
substrates as well ambient temperature and reaction time. No
product formation was observed in THF, acetonitrile and
DCE with or without iodine catalyst. When the reaction was
carried out with DMF 3c was obtained in low yield along
with side products. Similarly, reaction in DMSO under MW
irradiation afforded 30% yield. When the same reaction was
carried out in H2O afforded good yield of product.
Encouraged by this result, the reaction was performed in
water and repeated many times at different temperatures in a
sealed vessel under microwave heating, which resulted in the
respective products in good yields and the results are
presented in Table 1. Interestingly, the yields of products
increased from 40% to 70% as the temperature was raised
from 80 to 102 0C. It may be stated that microwave irradiation
With the optimized reaction conditions established, we
investigated the scope of this protocol. We first explored the
scope of reaction by using various methyl quinolines and β-
nitro styrene derivatives. The results are summarized in Table
2. As expected, various aromatic nitro styrenes worked well
under the reaction condition. Methyl quinolines with nitro
styrenes bearing electron releasing groups such as methoxy
and methyl, gave comparatively high yield (Table 2, entries 1,
2, 3, 4, 10 and 11), whereas electron withdrawing groups like
chloro, bromo gave low yield of products (Table 2, entries 6
and 7). Moreover, the heterocyclic nitro styrenes (Table 2,
entries 8 and 9) and 2-napthyl nitro styrene (Table 2, entry
12) still displayed high reactivity under the standard
conditions. However, 2-methyl pyridine and 4-methyl
pyridine did not participate under the standard reaction
condition. The yield of 3c was nearly same as 3k, indicating
that the nitro group on methyl quinoline had little influence
on the reaction.
0
of reaction mixture in aqueous medium at 102 C is the best
reaction condition.7 Moreover, by increasing the amount of 1a
from 1 to 1.5 eq. increased, the yield of product 3a to 70%.
Table 2: Actvation of methyl quinoline and Michael addition
to nitrostyrenesa
Ar
MW
Ar
NO2
NO2
H2O, 102 0
C
N
N
R
R
1
2
3
Time (min) Yieldb(%)
Ar (2)
Producta(3)
3a
Entry
1
R (1)
H
Scheme 2: A plausible mechanism of the reaction
MeO
2a
20
25
85
60
MeO
O
We presume that under microwave irradiation, the enamine
intermediate was generated via the requisite disruption of
aromaticity of 1. The Michael addition of the enamine
intermediate to nitrostyrene would afford the coupled adduct
(Scheme 2, Table 1).
In conclusion, we have developed an efficient microwave
assisted catalyst-free addition of methyl quinolines to β-Nitro
styrenes via sp3 C-H bond functionalisation. This green
protocol can be used in the drug discovery programme for the
rapid preparation of library of quinoline derivatives.
H
3b
2
2b
O
MeO
25
25
3
4
H
H
3c
3d
80
75
2c
Me
2d
2e
H
25
70
5
3e
Cl
Br
Acknowledgments
N N R thanks UGC for the award of a fellowship and Dr. A.
Kamal, Director IICT, for his support and encouragement
H
H
6
7
30
30
60
60
3f
2f
3g
2g
O
S
References
H
H
3h
3i
20
18
80
85
8
9
2h
2i
1. a) Kishor, P.; Jaganmohan, M. Org. Lett. 2012, 14, 6144;
b) Wendlant, A. E.; Suess, A. M.; Stahl, S. S. Angew.
Chem., Int. Ed., 2012, 51, 1; c) Wang, L.; Shen, L.; Zhi,
L.; Yongping, Y. Org. Lett. 2011, 13, 6137; d) Shibata,
Y.; Otake, Y.; Hirano, M., Tanaka, K. Org. Lett. 2011, 13,
6137; e) Newhouse, T.; Baran, S. P. Angew Chem. Int.
Ed. 2011, 50, 3362; f) Campos, K. R. Chem. Soc. Rev.
2007, 36, 1069.
2. a) Niu, R.; Xiao, J.; Liang, T.; Li, X. Org. Lett. 2012, 14,
676; b) Yang, Y.; Xie, C.; Zhang, Y. Org.Lett. 2012, 14,
957; c) Liu, J. Y.; Niu, H. Y.; Wu, S.; Qu, G. R.; Guo, H.
M. Chem. Commun. 2012, 48, 9723; d) Iglesias, A.;
Alverz, R.; De Lera, A. R.; Muniz, K. Angew. Chem., Int.
OMe
NO2
3j
25
25
20
80
75
10
11
2j
MeO
3k
NO2
NO2
2k
2l
3l
85
12
a all products were characterised by IR, 1HNMR, 13CNMR and Mass8
b
yield refers to pure produts after purification

Tetrahedron Letters
3
Ed., 2012, 51, 1; e) Rueping, M.; Tolstoluzhsky, N. Org.
Lett. 2011, 13, 1095; f) Komai, H.; Yoshino, T.;
Matsuguna, S.; Kanai, M. Org. Lett. 2011, 13, 1706; g)
Qian, B.; Xie, Y.; Huang, H. Org. Lett. 2011, 13, 2580; h)
Burton, M. P.; Morris, A. J. Org. Lett. 2010, 12, 5359; i)
Qian, B.; Guo, S.; Shao, J.; Zhu, Q.; Yang, L.; Xia, C.;
Huang, H. J. Am. Chem. Soc. 2010, 132, 3650; j) Tobisu,
M.; Chatani, N. Angew. Chem. Int. Ed. 2006, 45, 1683; k)
Kakiuchi, F.; Chatani, N. Adv. Synth. Catal. 2003, 345,
1077.
128.5, 127.4, 126.6, 126.2, 121.6, 119.2, 111.1, 110.7,
79.7, 55.6, 43.4, 42.2, 29.5; m/z (ESI); 353 [M+H]+.
2-(2-(benzo[d][1,3]dioxol-5-yl)-3-nitropropyl)quinoline
(3b) IR: νmax 2956, 2924, 2855, 1600, 1551, 1503, 1487,
1
1444, 1377, 1247, 1039, 934, 819, 751 cm-1; H NMR
(300 MHz, CDCl3): δ 8.01-8.11 (m, 2H), 7.65-7.81 (m,
2H), 7.45-7.55 (m, 1H), 7.28 (d, J = 3.02 Hz, 1H), 7.15 (d,
J = 8.3 Hz, 1H), 6.75 (s, 1H), 6.69 (s, 1H), 5.90 (s, 2H),
4.62-4.83 (m, 2H), 4.06-4.23 (m 1H), 3.31 (d, J = 7.5 Hz,
2H); 13C NMR (75 MHz, CDCl3): δ 158.3, 147.9, 147.7,
147.5, 136.6, 129.6, 129.4, 128.8, 127.5, 126.2, 125.6,
121.6, 120.8, 108.4, 107.6, 101.0, 79.8, 43.6, 42.3; m/z
(ESI); 307 [M+H]+.
3. Meshram, H. M.; Nageswara Rao, N.; Chandrasekhara
Rao, L.; Satish Kumar, N. Tetrahedron Lett. 2012, 53,
3963.
4. a) Iaroshenko, V. O.; Knepper, I.; Zahid, M.; Kuzora, R.;
Dudkin, S.; Villinger, A.; Langer, P. Org. Biomol.Chem.
2012, 10, 2955; b) Henry, D. Tetrahedron, 2004, 60,
6043; c) Lehn, J.-M. Science 2002, 295, 2400; d) Baxter,
P. N. W.; Lehn, J. M.; Fischer, J.; Youinou, M. T. Angew.
Chm. Int. Ed. 1994, 33, 2284.
5. a) De Rosa, M.; Soriente, A. Tetrahedron 2010, 66, 2981;
b) Vivek, P.; Varma, R. S. Tetrahedron Lett. 2007, 48,
8735; c) Sarah, M.; Alexandre, A. Org. Lett. 2006, 8,
3577; d) Kappe, C. O. Angew. Chm. Int. Ed. 2004, 43,
6250; e) Mats, L.; Christan, M.; Anders, H. Acc.Chem.
Res. 2002, 35, 717; f) Varma, R. S. Green. Chem. 1999, 1,
43.
6. a) Pateliya, M. H.; Veerababurao, K.; Chun-wei, K.;
Ching-Fa, Y. Tetrahedron Lett. 2008, 49, 7005; b) Khatik,
G. L.; Kumar, R.; Chakraborti, A. K. Org. Lett. 2006, 8,
2433; c) Kavala, V.; Samal, A. K.; Patel, B. K. ARKIVOC
2005, i, 20; d) Azizi, N.; Saidi, M. R. Org. Lett. 2005, 7,
3649; e) Maggi, R.; Bigi, F.; Carloni, S.; Mazzacani, A.;
Sartori, G. Green Chem. 2001, 3, 173; f) Li, C. J. Chem.
Rev. 1993, 93, 2023.
7. General procedure: A sealed 10 mL glass tube containing
nitrostyrene (1 equiv.), methyl quinoline (1.5 equiv.) and
water (3 mL) was placed in the cavity of a microwave
reactor and irradiated for appropriate time, at 1020C
(temperature monitored by built in infrared sensor), and
power 150 W. After cooling to room temperature by an
air-flow, the tube was removed from the rotor. The
reaction mixture was diluted with water and extracted with
ethyl acetate. The combined ethyl acetate extracts were
then dried over Na2SO4 and after removal of the solvent
the mixture was purified by (silica gel) column
chromatography (hexane/AcOEt, 80:20 as eluent) to give
pure products.
2-(2-(4-methoxyphenyl)-3-nitropropyl)quinoline (3c) IR:
νmax 2926, 2841, 1606, 1550, 1510, 1377, 1250, 1179,
1
1032, 830, 769 cm-1; H NMR (300 MHz, CDCl3): δ 8.04
(d, J = 8.4 Hz, 1H), 7.86-7.95 (m, 1H), 7.58-7.71 (m, 2H),
7.37-7.46 (m, 1H), 7.12 (d, J = 6.9 Hz, 2H), 6.99-7.07 (m,
1H), 6.70-6.79 (m, 2H), 4.60-4.81 (m, 2H), 4.09-4.21 (m,
1H), 3.63 (s, 3H), 3.27 (d, J = 6.6 Hz, 2H); 13C NMR (75
MHz, CDCl3): δ 158.5, 158.2, 147.3, 136.1, 130.8, 129.2,
128.4, 128.2, 127.2, 126.4, 125.8, 121.4, 113.8, 79.5, 54.6,
42.8, 41.9; m/z (ESI); 323 [M+H]+.
2-(3-nitro-2-p-tolylpropyl)quinoline (3d) IR: νmax 2924,
1
2854, 1599, 1551, 1507, 1428, 1377, 819, 749 cm-1; H
NMR (300 MHz, CDCl3): δ 8.03 (dd, J = 8.8 Hz, J = 1.7
Hz, 2H), 7.65-7.79 (m, 2H), 7.45-7.53 (m, 1H), 7.24-7.34
(m, 1H), 7.05-7.17 (m, 4H), 4.66-4.85 (m, 2H), 4.11-4.23
(m, 1H), 3.34 (d, J = 7.7 Hz,.2H), 2.28 (s, 3H); 13C NMR
(75 MHz, CDCl3): δ 158.5, 147.7, 137.2, 136.5, 136.2,
129.6, 129.5, 128.9, 127.4, 127.2, 126.8, 126.1, 125.7,
121.9, 121.6, 79.7, 43.4, 42.4, 29.6; m/z (ESI); 307
[M+H]+.
2-(3-nitro-2-phenylpropyl)quinoline (3e) IR: νmax 2956,
2924, 2854, 1599, 1551, 1501, 1457, 1376, 1261, 822, 752
1
cm-1; H NMR (300 MHz, CDCl3): δ 8.03 (dd, J = 14.3
Hz, J = 8.1 Hz, 2H), 7.64-7.79 (m, 2H), 7.50 (t, J = 6.9
Hz, 1H), 7.20-7.32 (m, 5H), 7.11 (d, J = 8.3 Hz, 1H),
4.68-4.89 (m, 2H), 4.14-4.27 (m, 1H), 3.35 (d, J = 7.3 Hz,
2H); 13C NMR (75 MHz, CDCl3): δ 158.3, 147.6, 139.2,
136.5, 129.6, 128.7, 127.5, 127.4, 127.3, 126.7, 126.7,
126.1, 125.7, 121.9, 121.5, 79.5, 43.7, 42.2; m/z (ESI);
293 [M+H]+.
2-(2-(4-chlorophenyl)-3-nitropropyl)quinoline (3f) IR:
νmax 2924, 2855, 1598, 1552, 1497, 1376, 1093, 826, 752
1
cm-1; H NMR (300 MHz, CDCl3): δ 7.99-8.10 (m, 2H),
7.65-7.81 (m, 2H), 7.50 (t, J = 7.5 Hz, 1H), 7.08-7.35 (m,
5H), 4.66-4.88 (m, 2H), 4.16-4.28 (m, 1H), 3.24-3.38 (m,
2H); 13C NMR (75 MHz, CDCl3): δ 157.8, 147.7, 137.7,
136.6, 136.4, 129.7, 128.9, 128.8, 127.5, 127.4, 126.3,
121.9, 121.5, 79.3, 42.0, 43.0; m/z (ESI); 327 [M+H]+.
2-(2-(4-bromophenyl)-3-nitropropyl)quinoline (3g) IR:
νmax 2924, 2853, 1598, 1551, 1488, 1428, 1377, 1073,
8. Spectral data of representative compounds:
12-(2-(3, 4-dimethoxyphenyl)-3-nitropropyl)quinoline (3a)
IR: νmax 3006, 2927, 1597, 1550, 1514, 1461, 1427, 1378,
1262, 1144, 1026, 823 cm-1; 1H NMR (300 MHz, CDCl3):
δ 8.04 (dd, J = 8.1 Hz, J = 2.8 Hz, 2H), 7.76 (d, J = 8.1
Hz, 1H), 7.67-7.74 (m, 1H), 7.51 (t, J = 7.9 Hz, 1H), 7.14
(d, J = 8.4 Hz, 1H), 6.77-6.81 (m, 2H), 6.72 (d, J = 1.5 Hz,
1H), 4.69-4.85 (m, 2H), 4.10-4.22 (m, 1H), 3.81 (s, 3H),
3.77 (s, 3H), 3.36 (d, J = 7.7 Hz, 2H); 13C NMR (75 MHz,
CDCl3): δ 158.3, 148.8, 148.2, 147.4, 136.6, 131.4, 129.6,
1
1010, 826, 756 cm-1; H NMR (300 MHz, CDCl3): δ 8.02
(t, J = 8.4 Hz, 2H), 7.66-7.77 (m, 2H), 7.45-7.53 (m, 1H),
7.38 (d, J = 8.3 Hz, 2H), 7.11 (dd, J = 8.3 Hz, J = 3.3 Hz,
3H), 4.66-4.87 (m, 2H), 4.16-4.27 (m, 1H), 3.23-3.38 (m,
2H); 13C NMR (75 MHz, CDCl3): δ 157.8, 147.6, 138.2,

4
Tetrahedron Letters
136.6, 131.2, 131.3, 129.6, 129.1, 128.7, 127.5, 126.7,
126.2, 121.5, 121.4, 79.2, 43.0, 41.8; m/z (ESI); 373
[M+H]+.
2-(2-(furan-2-yl)-3-nitropropyl)quinoline (3h) IR: νmax
2924, 2854, 1599, 1553, 1504, 1428, 1377, 1013, 824,743
cm-1; 1H NMR (300 MHz, CDCl3): δ ; 8.04 (d, J = 8.4 Hz,
2H), 7.67-7.81 (m, 2H), 7.51 (t, J = 7.5 Hz, 1H), 7.33-7.38
(m, 1H), 7.15 (d, J = 8.3 Hz, 1H), 6.22-6.26 (m, 1H), 6.09
(d, J = 3.2 Hz, 1H), 4.71-4.86 (m, 2H), 4.32-4.43 (m, 1H),
3.30-3.49 (m, 2H); 13C NMR (75 MHz, CDCl3): δ 157.9,
152.1, 147.7, 142.1, 136.5, 129.6, 128.4, 127.4, 126.2,
121.5, 110.2, 107.3, 77.4, 39.6, 37.4; m/z (ESI); 283
[M+H]+.
2-(3-nitro-2-(thiophen-2-yl)propyl)quinoline (3i) IR: νmax
2924, 2854, 1558, 1550, 1502, 1428, 1376, 824, 701 cm-1;
1H NMR (300 MHz, CDCl3): δ 8.04 (t, J = 8.1 Hz, 2H),
7.66-7.79 (m, 2H), 7.50 (t, J = 7.1 Hz, 1H), 7.13-7.20 (m,
2H), 6.87 (d, J = 3.3 Hz, 2H), 4.67-4.90 (m, 2H), 4.53-
4.64 (m, 1H), 3.34-3.48 (m, 2H); 13C NMR (75 MHz,
CDCl3): δ 157.8, 147.7, 142.2, 136.5, 129.6, 128.8, 127.4,
126.8, 126.2, 125.3, 124.4, 121.6, 80.0, 42.9, 38.9; m/z
(ESI); 299 [M+H]+.
2-(2-(naphthalen-1-yl)-3-nitropropyl)-8-nitroquinoline
(3j) IR: νmax 2922, 2854, 1624, 1600, 1549, 1526, 1427,
1374, 750 cm-1; 1H NMR (300 MHz, CDCl3): δ 8.05 (d, J
= 8.4 Hz, 1H), 7.98 (d, J = 7.3 Hz, 1H), 7.92 (d, J = 8.1
Hz, 1H), 7.71 (m, 4H), 7.52 (t, J = 7.8 Hz, 1H), 7.37-7.46
(m, 3H), 7.28 (d, J = 8.4 Hz, 1H), 4.86-5.11 (m, 2H), 4.40-
5.11 (m, 1H), 3.45-3.60 (m, 2H); 13C NMR (75 MHz,
CDCl3): δ 161.1, 147.9, 138.8, 136.4, 136.3, 133.3, 132.7,
131.5, 128.7, 127.8, 127.5, 126.9, 126.2, 126.0, 125.1,
124.8, 123.6, 123.5, 79.5, 42.7, 41.5; m/z (ESI); 388
[M+H]+.
2-(2-(4-methoxyphenyl)-3-nitropropyl)-8-nitroquinoline
(3k) IR: νmax 2924, 2854, 1590, 1549, 1520, 1423, 1372,
1
770 cm-1; H NMR (300 MHz, CDCl3): δ 8.09 (d, J = 8.3
Hz, 1H), 7.97 (t, J = 9.2 Hz, 2H), 7.55 (t, J = 7.9 Hz, 1H),
7.27 (d, J = 9.0 Hz, 1H), 7.16 (d, J = 8.4 Hz, 2H), 6.80 (d,
J = 8.3 Hz, 2H), 4.71-4.99 (m, 2H), 4.11-4.28 (m, 1H),
3.74 (s, 3H), 3.30-3.48 (m, 2H); 13C NMR (75 MHz,
CDCl3): δ 158.8, 147.9, 138.8, 136.2, 131.5, 131.0, 128.7,
128.5, 127.5, 124.8, 123.5, 114.2, 79.7, 55.1, 42.1, 41.8;
m/z (ESI); 368 [M+H]+.
2-(2-(2-methoxyphenyl)-3-nitropropyl)-8-nitroquinoline
(3l) IR: νmax 2924, 2842, 1623, 1601, 1550, 1495, 1462,
1378, 1246, 1026, 757 cm-1; 1H NMR (300 MHz, CDCl3):
δ 8.01 (d, J = 7.5 Hz, 1H), 7.87 (t, J = 8.3 Hz, 2H), 7.44 (t,
J = 8.3 Hz, 1H), 7.25 (d, J = 8.3 Hz, 1H), 7.09-7.19 (m,
2H), 6.75-6.86 (m, 2H), 4.91-5.04 (m, 2H), 4.39-4.51 (m,
1H), 3.82 (s, 3H), 3.45 (d, J = 7.5 Hz, 2H); 13C NMR (75
MHz, CDCl3): δ 161.7, 157.0, 147.5, 138.4, 135.9, 131.3,
129.0, 128.4, 127.2, 126.4, 124.4, 123.3, 123.1, 120.3,
110.6, 77.6, 55.1, 39.5, 38.8; m/z (ESI); 368 [M+H]+.