First synthesis of bromo and chloro derivatives of baylis-hillman adducts derived from nitroolefins: Application towards the synthesis of a dendrimer core

Article abstract of DOI:10.1055/s-0030-1258409

For the first time Baylis-Hillman adducts derived from nitroolefins have been conveniently transformed into a novel class of building blocks, 1-[(E)-3-bromo-2-nitroprop-1-enyl]arenes and 1-[(E)-3-chloro-2-nitroprop-1-enyl] arenes, in very good yields via

Full text of DOI:10.1055/s-0030-1258409

PAPER
611
First Synthesis of Bromo and Chloro Derivatives of Baylis–Hillman Adducts
Derived from Nitroolefins: Application towards the Synthesis of a Dendrimer
Core
S
ynthesis of Bromo an
a
d
C
hloro
D
n
erivative
s
of
i
Baylis
c
kdducts am Bakthadoss,* Nagappan Sivakumar, Anthonisamy Devaraj
Dept. of Organic Chemistry, University of Madras, Guindy Campus, Chennai 600 025, India
Fax +91(44)22352494; E-mail: bhakthadoss@yahoo.com
Received 23 November 2010; revised 9 December 2010
ful starting materials for a variety of applications in organ-
Abstract: For the first time Baylis–Hillman adducts derived from
nitroolefins have been conveniently transformed into a novel class
of building blocks, 1-[(E)-3-bromo-2-nitroprop-1-enyl]arenes and
1-[(E)-3-chloro-2-nitroprop-1-enyl]arenes, in very good yields via
ic synthesis. Baylis–Hillman adducts and its derived
compounds are extensively utilized in the synthesis of bi-
ologically active molecules, heterocycles, and many natu-
an SN2 reaction using simple reaction conditions. Further applica- ral products. In particular bromo and acetate derivatives
tion of these compounds has been demonstrated for the synthesis of
of Baylis–Hillman adducts are widely utilized for various
organic transformations.1–9 For example, Basavaiah and
tris[(E)-2-nitro-3-arylallyl]amines as dendrimer cores.
Key words: Baylis–Hillman reaction, ammonium acetate, nitroalk-
enes, iron(III) chloride, hydrobromic acid
co-workers successfully synthesized bonducellin methyl
ether, a natural product isolated from Caesalpinia bondu-
cella and Caesalpinia pulcherrima. They also synthesized
antifungal agent using the bromo derivative of a Baylis–
The Baylis–Hillman reaction, an exquisite reaction as Hillman adduct as a starting material.10 Many reports are
simple starting materials are converted into densely func- available in the literature demonstrating the synthetic util-
tionalized products1–3 in a catalytic process without gener- ity of bromo derivatives of Baylis–Hillman adducts in the
ating waste or byproducts, has made great progress since synthesis of b-lactams, b-azido esters, polyfunctionalized
Baylis and Hillman first reported the reaction of acetalde- decalins, urethane N-carboxyanhydrides11–14 etc. Based
hyde with ethyl acrylate or acrylonitrile in the presence of on these reports, we envisaged that the bromo compounds
a catalytic amount of a strong nitrogen Lewis base such as derived from nitroolefins will also serve as excellent
1,4-diazabicyclo[2.2.2]octane (DABCO) in 1972.1,2
building blocks for the synthesis of a wide variety of use-
ful compounds. Triggered by this idea, we decided to pre-
pare the bromo compound derived from nitroolefins,
which will open new avenues for synthetic transforma-
tions. In continuation of our research interest in the field
of Baylis–Hillman chemistry,15–20 we planned to synthe-
size 1-[(E)-3-bromo-2-nitroprop-1-enyl]arenes 3 which
are very useful starting material for various transforma-
tions.
During the past ten years the Baylis–Hillman reaction has
seen an enormous growth in terms of the components such
as electrophile, activated olefin, and catalyst. A variety of
activated olefins have been explored by various research
groups, however nitroolefins are not frequently utilized.
So far there is no report available in the literature on the
synthesis of Baylis–Hillman adducts derived from alde-
hydes and nitroethene except the initial report by Baylis
and Hillman. The reason why nitroethene is unexplored It occurs to us that the target compound i.e. 1-[(E)-3-bro-
may be due to its higher reactivity, which would lead to mo-2-nitroprop-1-enyl]benzene (3a) can be easily synthe-
polymerization. Though various trisubstituted olefins de- sized directly by treating a-methyl-a-nitrostyrene with N-
rived from Baylis–Hillman adducts using acrylates, acry- bromosuccinimide under allylic radical bromination con-
lonitrile, or methyl vinyl ketone have been successfully ditions. Unfortunately we did not obtain the desired bro-
synthesized and utilized for various organic transforma- mo compound 3a (Scheme 1).
tions, the synthesis of trisubstituted allyl halides derived
from nitroolefins has not been reported in the literature
and applications of these trisubstituted allyl halides have
yet to be explored. Therefore, we have undertaken a re-
search program for the synthesis and examination of the
possible applications of trisubstituted allyl halides derived
from nitroolefins in various organic reactions. We envis-
aged that the bromo derivative of Baylis–Hillman adducts
derived from aldehydes and nitroethenes may be very use-
NO2
Br
NO2
NBS
AIBN
3a
Scheme 1
To find an alternative method for the synthesis of bromo
compound 3a, we decided to utilize (E)-2-nitro-3-phenyl-
prop-2-en-1-ol (2a), which can be synthesized by the
treatment of a-nitrostyrene (1a) with aqueous formalde-
hyde in the presence of imidazole and anthranilic acid in
tetrahydrofuran as a solvent.21 We envisaged that the syn-
SYNTHESIS 2011, No. 4, pp 0611–0618
x
x
.
x
x
.2
0
1
1
Advanced online publication: 12.01.2011
DOI: 10.1055/s-0030-1258409; Art ID: Z29010SS
© Georg Thieme Verlag Stuttgart · New York

612
M. Bakthadoss et al.
PAPER
thesized compound, namely (E)-2-nitro-3-phenylprop-2- atives 3b–n in very good yields (76–93%, Table 1). To
en-1-ol (2a), can be conveniently transformed into the further understand the reaction, we decided to synthesize
corresponding bromo derivative 3a by treatment with bro- the chloro derivatives from the corresponding Baylis–
minating agents. Accordingly, the Baylis–Hillman adduct Hillman adducts under mild reaction conditions. The
2a, derived from nitroolefin and formaldehyde, was treat- treatment of Baylis–Hillman adduct 2a–e,l,n with
ed with aqueous hydrobromic acid (48%) with dichlo- iron(III) chloride in dichloromethane over a period of six
romethane as the solvent to yield successfully 1-[(E)-3- hours successfully provided the desired 1-[(E)-3-choloro-
bromo-2-nitroprop-1-enyl]benzene (3a) in 62% yield 2-nitroprop-1-enyl]arenes 4a–e,l,n in 73–85% yields
1
(Table 1, entry 1).
(Table 2). The H NMR spectrum of the compound 4a
showed the CH2 protons as a singlet at d = 4.79 ppm, the
olefinic proton as a singlet at d = 8.28 ppm, and the aro-
matic protons as multiplets in the region of d = 7.45–7.59.
Thus we have successfully synthesized trisubstituted allyl
bromides 3a–n and chlorides 4a–e,l,n bearing nitro group
on the olefinic carbon in very good yields (Tables 1
and 2).
1
The H NMR spectrum of the compound 3a showed the
CH2 protons as a singlet at d = 4.54 ppm, the olefinic pro-
ton as a singlet at d = 8.15 ppm, and the aromatic protons
as multiplets in the region of d = 7.44–7.54 ppm. Encour-
aged by this result, we prepared a variety of Baylis–
Hillman adducts 2b–n derived from nitroolefins 1a–n and
successfully converted them into the desired bromo deriv-
Table 1 Synthesis of Trisubstituted Allyl Bromides
O
H
H
imidazole (100 mol%)
anthranilic acid (10 mol%)
THF, r.t.
HBr, concd H2SO4
NO2
NO2
CH2Cl2
R
R
NO2
R
OH
2a–n
Br
1a–n
3a–n
Entry
1
R
Substrate
1a
Time (h)
24
BH adducta,b Yieldc (%)
Time (h)
24
Productd
Yieldb,c (%)
Ph
2a
2b
2c
2d
2e
2f
50 (50)
70
3a
3b
3c
3d
3e
3f
62
80
84
82
86
80
90
92
92
80
76
78
90
93
2
2-naphthyl
2-MeC6H4
4-MeC6H4
4-EtC6H4
1b
28
12
3
1c
24
52
24
4
1d
24
42
24
5
1e
24
46
24
6
4-i-PrC6H4
2-MeOC6H4
4-MeOC6H4
1f
24
52
24
7
1g
16
2g
2h
2i
50
12
3g
3h
3i
8
1h
15
56 (50)
44 (46)
30 (25)
55
12
9
3,4-(MeO)2C6H3
4-FC6H4
1i
36
12
10
11
12
13
14
1j
30
2j
24
3j
2-ClC6H4
3-ClC6H4
2-furyl
1k
24
2k
2l
24
3k
3l
1l
24
43
24
1m
24
2m
70 (71)
60 (56)
12
3m
3n
2-thienyl
1n
15
2n
12
a All reactions were carried out using a-nitrostyrene 1a–n (10 mmol) at r.t.21
b All products gave satisfactory IR, 1H and 13C NMR, and MS data.
c Yield of pure products 2a–n/3a–n obtained after column chromatography, the yield in the parenthesis corresponds to the yield reported in the
literature.21
d All reactions were carried out with BH adduct 2a–n (4 mmol) at r.t. for the specified reaction time.
Synthesis 2011, No. 4, 611–618 © Thieme Stuttgart · New York

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Synthesis of Bromo and Chloro Derivatives of Baylis–Hillman Adducts
613
Table 2 Synthesis of Trisubstituted Allyl Chlorides
tons as a singlet at d = 8.27 ppm, and the aromatic protons
as multiplets in the region of d = 7.26–7.75 ppm. A variety
of other bromo derivatives were also conveniently con-
verted into the corresponding triallylamines 5 in 61–80%
yields (Table 3).
NO2
NO2
R
R
+
FeCl3
CH2Cl2
Cl
4a–e,l,n
OH
2a–e,l,n
In conclusion, we have successfully developed a short and
simple protocol for the synthesis of bromo and chloro de-
rivatives of Baylis–Hillman adducts derived from ni-
troolefins in good yields. This novel class of bromo and
chloro derivatives can be utilized as building blocks for
wide variety of organic compounds. We also developed a
facile method for the transformation of these bromides
into an interesting and novel class of trisubstituted triallyl-
amines which are core unit of dendrimers, thus demon-
strating the synthetic utility of the bromo derivatives of
the Baylis–Hillman adducts. Hence this novel protocol
opens new opportunities for the preparation of libraries of
wide variety of new molecules. Further utilization of the
bromo and chloro derivatives of the Baylis–Hillman ad-
ducts and trisubstituted triallylamines for the synthesis of
heterocyclic compounds is in progress in our laboratory.
Entry
R
BH adduct Producta
Yieldb,c (%)
1
2
3
4
5
6
7
Ph
2a
2b
2c
2d
2e
2l
4a
4b
4c
4d
4e
4l
73
74
85
84
78
82
80
2-naphthyl
2-MeC6H4
4-MeC6H4
4-EtC6H4
3-ClC6H4
2-thienyl
2n
4n
a All reactions were carried out with BH adduct 2 (2 mmol), r.t., 6 h.
b Isolated yield of the pure product after column chromatography.
c All products gave satisfactory IR, 1H and 13C NMR, and MS data.
Table 3 Synthesis of Trisubstituted Triallylamines
All reagents were purchased from commercial sources and used
without further purification. Solvents were distilled prior to use.
Column chromatography was performed on silica gel. IR spectra
NO2
R
NO2
MeOH
r.t.
O2N
R
+
NH4OAc
1
N
R
were recorded on an FTIR-8300 Shimadzu spectrophotometer. H
NMR (300 MHz) and 13C NMR (75 MHz) were recorded on a Bruk-
er spectrometer using CDCl3 as solvent and TMS as an internal
standard; chemical shifts are reported in d (ppm). Mass spectra were
recorded on a Jeol-JMS-DX 303 HF mass spectrometer. Elemental
analyses were recorded on a Perkin-Elmer 240C-CHN analyzer.
Melting points are uncorrected. Thin-layer chromatography (TLC)
was performed using glass plates coated with silica gel (ACME,
254F). Spots were visualized using iodine vapour and UV lamp.
Br
R
3a–e,g–i,m,n
NO2
5a–e,g–i,m,n
Entry
R
Substrate Producta Yieldb,c (%)
1
2
Ph
3a
3b
3c
3d
3e
3g
3h
3i
5a
5b
5c
5d
5e
5g
5h
5i
80
61
75
74
62
73
68
71
69
80
2-naphthyl
2-MeC6H4
4-MeC6H4
4-EtC6H4
(E)-2-Nitro-3-phenylprop-2-en-1-ol (2a); Typical Procedure21
To a stirred soln of a-nitrostyrene (1a, 1.50 g, 10 mmol) in THF (20
mL) at r.t. was added imidazole (0.68 g, 1 equiv) followed by an-
thranilic acid (0.14 g, 10 mol%). Aq formaldehyde (38%, 20 mL,
excess) was then added and the mixture was stirred at r.t. for the pe-
riod specified in Table 1. On completion of the reaction (TLC anal-
ysis), the mixture was acidified with 5 M HCl (20 mL) and the
aqueous layer was extracted with EtOAc (3 × 25 mL). The com-
bined organic layers were washed with brine (50 mL), dried (anhyd
Na2SO4), and concentrated in vacuo. The residue was purified by
column chromatography (silica gel, EtOAc–hexanes, 0–25%, gra-
dient elution) to afford pure 2a (0.90 g, 50%) as a yellow oil.
IR (KBr): 3423, 1653, 1522, 1326, 1023, 695 cm–1.
1H NMR (300 MHz, CDCl3): d = 2.61 (s, 1 H), 4.71 (d, J = 4.2 Hz,
2 H), 7.48–7.58 (m, 5 H), 8.22 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 56.62, 129.14, 130.19, 130.96,
131.31, 137.67, 149.44.
3
4
5
6
2-MeOC6H4
4-MeOC6H4
7
8
3,4-(MeO)2C6H3
2-furyl
9
3m
5m
10
2-thienyl
3n
5n
a All reactions were carried out with BH bromide 3 (2 mmol), r.t.
b Yield of the pure product obtained after washing with Et2O.
c All products gave satisfactory IR, 1H and 13C NMR, and MS data.
MS: m/z = 179 (M+).
The efficiency of this methodology has been demonstrat-
ed via the synthesis of triallylamines 5, which can be uti-
lized as a core for the synthesis of dendrimer. Treatment
of 1-[(E)-3-bromo-2-nitroprop-1-enyl]benzene (3a) with
ammonium acetate successfully provided the desired C3
symmetric trisubstituted triallylamine 5a in 80% yield.
Anal. Calcd for C9H9NO3: C, 60.33; H, 5.06; N, 7.82. Found: C,
60.37; H, 5.08; N, 7.80.
(E)-3-(Naphthalen-2-yl)-2-nitroprop-2-en-1-ol (2b)
Yield: 1.60 g (70%); mp 80–82 °C.
IR (KBr): 3425, 1652, 1517, 1339, 1218, 704 cm–1.
1H NMR (300 MHz, CDCl3): d = 2.47 (s, 1 H), 4.67 (s, 2 H), 7.53–
8.00 (m, 7 H), 8.81 (s, 1 H).
1
The H NMR spectrum of the compound 5a showed the
CH2 protons as a singlet at d = 3.91 ppm, the olefinic pro-
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M. Bakthadoss et al.
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13C NMR (75 MHz, CDCl3): d = 56.88, 123.94, 125.50, 126.42,
126.82, 127.47, 128.29, 128.47, 128.92, 131.38, 131.52, 133.40,
135.72, 150.58.
13C NMR (75 MHz, CDCl3): d = 55.67, 56.72, 110.85, 120.44,
120.95, 130.70, 132.81, 133.90, 148.96, 158.38.
MS: m/z = 209 (M+).
MS: m/z = 229 (M+).
Anal. Calcd for C10H11NO4: C, 57.41; H, 5.30; N, 6.70. Found: C,
57.39; H, 5.24; N, 6.76.
Anal. Calcd for C13H11NO3: C, 68.11; H, 4.84; N, 6.11. Found: C,
68.43; H, 4.57; N, 6.18.
(E)-3-(4-Methoxyphenyl)-2-nitroprop-2-en-1-ol (2h)
Yield: 1.17 g (56%); mp 75–77 °C.
(E)-2-Nitro-3-(2-tolyl)prop-2-en-1-ol (2c)
Yellow oil; yield: 0.96 g (52%).
IR (KBr): 3445, 1653, 1528, 1338, 1023, 695 cm–1.
1H NMR (300 MHz, CDCl3): d = 2.38 (s, 3 H), 2.68 (s, 1 H), 4.62
(s, 2 H), 7.26–7.46 (m, 4 H), 8.33 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 19.99, 56.54, 126.48, 129.45,
130.55, 130.59, 130.76, 136.32, 138.19, 149.80.
MS: m/z = 193 (M+).
IR (KBr): 3427, 1643, 1512, 1460, 1025, 715 cm–1.
1H NMR (300 MHz, CDCl3): d = 3.25 (s, 1 H), 3.85 (s, 3 H), 4.72
(s, 2 H), 6.96–7.58 (m, 4 H), 8.15 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 55.49, 56.69, 114.72, 123.67,
132.62, 137.98, 147.37, 162.12.
MS: m/z = 209 (M+).
Anal. Calcd for C10H11NO4: C, 57.41; H, 5.30; N, 6.70. Found: C,
57.46; H, 5.33; N, 6.64.
Anal. Calcd for C10H11NO3: C, 62.17; H, 5.74; N, 7.25. Found: C,
62.23; H, 5.71; N, 7.30.
(E)-3-(3,4-Dimethoxyphenyl)-2-nitroprop-2-en-1-ol (2i)
Yield: 1.05 g (44%); mp 100–102 °C.
(E)-2-Nitro-3-(4-tolyl)prop-2-en-1-ol (2d)
Yield: 0.80 g (42%); mp 49–52 °C.
IR (KBr): 3436, 1648, 1521, 1460, 1021, 702 cm–1.
1H NMR (300 MHz, CDCl3): d = 2.42 (s, 3 H), 2.57 (t, J = 7.2 Hz,
1 H), 4.71 (d, J = 7.2 Hz, 2 H), 7.26–7.48 (m, 4 H), 8.20 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 21.55, 56.76, 128.44, 129.92,
130.38, 137.92, 141.83, 148.67.
MS: m/z = 193 (M+).
IR (KBr): 3430, 1660, 1528, 1478, 1022, 720 cm–1.
1H NMR (300 MHz, CDCl3): d = 3.05 (s, 1 H), 3.92 (s, 3 H), 3.94
(s, 3 H), 4.75 (s, 2 H), 6.94–7.25 (m, 3 H), 8.17 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 55.96, 56.01, 56.79, 111.31,
112.95, 123.95, 124.88, 147.55, 149.24, 151.77.
MS: m/z = 239 (M+).
Anal. Calcd for C11H13NO5: C, 55.23; H, 5.48; N, 5.86. Found: C,
55.27; H, 5.51; N, 5.81.
Anal. Calcd for C10H11NO3: C, 62.17; H, 5.74; N, 7.25. Found: C,
62.22; H, 5.78; N, 7.19.
(E)-3-(4-Fluorophenyl)-2-nitroprop-2-en-1-ol (2j)
Yield: 0.59 g (30%); mp 54–56 °C.
(E)-3-(4-Ethylphenyl)-2-nitroprop-2-en-1-ol (2e)
Yellow oil; yield: 0.95 g (46%).
IR (KBr): 3233, 1643, 1590, 1321, 1093, 723 cm–1.
1H NMR (300 MHz, CDCl3): d = 1.27 (t, J = 7.5 Hz, 3 H), 2.72 (q,
J = 7.5 Hz, 2 H), 2.78 (s, 1 H), 4.74 (s, 2 H), 7.26–7.82 (m, 4 H),
8.20 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 15.17, 28.83, 56.53, 128.70,
130.05, 130.55, 137.92, 147.98, 148.75.
MS: m/z = 207 (M+).
IR (KBr): 3458, 1653, 1560, 1394, 1053, 755 cm–1.
1H NMR (300 MHz, CDCl3): d = 2.64 (s, 1 H), 4.68 (s, 2 H), 7.15–
7.62 (m, 4 H), 8.18 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 56.48, 116.32, 127.45, 132.48,
136.69, 149.17, 162.58, 165.94.
MS: m/z = 197 (M+).
Anal. Calcd for C9H8FNO3: C, 54.83; H, 4.09; N, 7.10. Found: C,
54.88; H, 4.12; N, 7.07.
Anal. Calcd for C11H13NO3: C, 63.76; H, 6.32; N, 6.76. Found: C,
63.82; H, 6.36; N, 6.67.
(E)-3-(2-Chlorophenyl)-2-nitroprop-2-en-1-ol (2k)
Yellow oil; yield: 1.17 g (55%).
(E)-3-(4-Isopropylphenyl)-2-nitroprop-2-en-1-ol (2f)
Yellow oil; yield: 1.15 g (52%).
IR (KBr): 3300, 1651, 1590, 1310, 1093, 715 cm–1.
1H NMR (300 MHz, CDCl3): d = 1.28 (d, J = 6.9 Hz, 6 H), 2.68 (s,
1 H), 2.96 (sept, J = 6.9 Hz, 1 H), 4.72 (s, 2 H), 7.26–7.52 (m, 4 H),
8.20 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 23.68, 34.16, 56.77, 127.32,
128.79, 130.52, 137.87, 148.74, 152.60.
IR (KBr): 3448, 1643, 1528, 1368, 1033, 715 cm–1.
1H NMR (300 MHz, CDCl3): d = 3.40 (s, 1 H), 4.67 (s, 2 H), 7.27–
7.85 (m, 4 H), 8.11 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 56.30, 128.17, 129.82, 129.87,
130.42, 130.88, 134.49, 135.52, 136.10.
MS: m/z = 213 (M+), 215 (M+ + 2).
Anal. Calcd for C9H8ClNO3: C, 50.60; H, 3.77; N, 6.56. Found: C,
50.65; H, 3.70; N, 6.58.
MS: m/z = 221 (M+).
Anal. Calcd for C12H15NO3: C, 65.14; H, 6.83; N, 6.33. Found: C,
65.19; H, 6.87; N, 6.25.
(E)-3-(3-Chlorophenyl)-2-nitroprop-2-en-1-ol (2l)
Yield: 0.60 g (43%); yellow oil.
IR (KBr): 3442, 1647, 1530, 1363, 1036, 720 cm–1.
1H NMR (300 MHz, CDCl3): d = 3.40 (s, 1 H), 4.62 (s, 2 H), 7.35–
8.01 (m, 4 H), 8.36 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 56.60, 126.70, 127.40, 130.01,
130.94, 131.44, 131.95, 132.37, 133.44.
(E)-3-(2-Methoxyphenyl)-2-nitroprop-2-en-1-ol (2g)
Yellow oil; yield: 1.05 g (50%).
IR (KBr): 3430, 1643, 1512, 1305, 1025, 705 cm–1.
1H NMR (300 MHz, CDCl3): d = 2.92 (q, J = 6.6 Hz, 1 H), 3.89 (s,
3 H), 4.66 (d, J = 6.6 Hz, 2 H), 6.94–7.55 (m, 4 H), 8.43 (s, 1 H).
Synthesis 2011, No. 4, 611–618 © Thieme Stuttgart · New York

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Synthesis of Bromo and Chloro Derivatives of Baylis–Hillman Adducts
615
MS: m/z = 213 (M+), 215 (M+ + 2).
1-[(E)-3-Bromo-2-nitroprop-1-enyl]-2-methylbenzene (3c)
Yield: 0.85 g (84%); mp 92–94 °C.
IR (KBr): 1635, 1526, 1328 cm–1.
Anal. Calcd for C9H8ClNO3: C, 50.60; H, 3.77; N, 6.56. Found: C,
50.67; H, 3.72; N, 6.62.
1H NMR (300 MHz, CDCl3): d = 2.37 (s, 3 H), 4.53 (s, 2 H), 7.29–
(E)-3-(Furan-2-yl)-2-nitroprop-2-en-1-ol (2m)
Yield: 1.18 g (70%); mp 88–90 °C.
IR (KBr): 3349, 1645, 1512, 1469, 1015, 725 cm–1.
1H NMR (300 MHz, CDCl3): d = 2.75 (s, 1 H), 5.04 (d, J = 4.8 Hz,
2 H), 6.61–7.71 (m, 3 H), 7.88 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 56.70, 113.37, 122.19, 122.76,
145.68, 146.90, 147.67.
7.61 (m, 4 H), 8.35 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 20.01, 23.05, 126.70, 128.17,
130.58, 130.85, 131.00, 136.14, 138.61, 147.44.
MS: m/z = 256 (M+), 257 (M+ + 1).
Anal. Calcd for C10H10BrNO2: C, 46.90; H, 3.94; N, 5.47. Found: C,
46.87; H, 3.90; N, 5.50.
MS: m/z = 169 (M+).
1-[(E)-3-Bromo-2-nitroprop-1-enyl]-4-methylbenzene (3d)
Yield: 0.83 g (82%); mp 110–112 °C.
IR (KBr): 1638, 1522, 1325 cm–1.
Anal. Calcd for C7H7NO4: C, 49.71; H, 4.17; N, 8.28. Found: C,
49.76; H, 4.15; N, 8.35.
1H NMR (300 MHz, CDCl3): d = 2.44 (s, 3 H), 4.65 (s, 2 H), 7.26–
(E)-2-Nitro-3-(thiophen-2-yl)prop-2-en-1-ol (2n)
Yield: 1.11 g (60%); mp 104–106 °C.
IR (KBr): 3335, 1643, 1518, 1338, 1023, 715 cm–1.
1H NMR (300 MHz, CDCl3): d = 2.74 (t, J = 6.9 Hz, 1 H), 4.91 (d,
J = 6.9 Hz, 2 H), 7.18–7.72 (m, 3 H), 8.31 (s, 1 H).
7.55 (m, 4 H), 8.23 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 21.67, 23.57, 128.33, 130.27,
130.61, 137.74, 142.39, 145.94.
MS: m/z = 256 (M+), 257 (M+ + 1).
Anal. Calcd for C10H10BrNO2: C, 46.90; H, 3.94; N, 5.47. Found: C,
46.85; H, 3.89; N, 5.56.
13C NMR (75 MHz, CDCl3): d = 56.72, 128.65, 130.39, 133.50,
133.55, 136.27, 146.18.
MS: m/z = 185 (M+).
1-[(E)-3-Bromo-2-nitroprop-1-enyl]-4-ethylbenzene (3e)
Yield: 0.93 g (86%); mp 118–120 °C.
IR (KBr): 1663, 1514, 1351 cm–1.
Anal. Calcd for C7H7NO3S: C, 45.40; H, 3.81; N, 7.56. Found: C,
45.45; H, 3.76; N, 7.59.
1H NMR (300 MHz, CDCl3): d = 1.28 (t, J = 7.8 Hz, 3 H), 2.73 (q,
J = 7.5 Hz, 2 H), 4.66 (s, 2 H), 7.36–7.58 (m, 4 H), 8.24 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 15.10, 23.57, 28.91, 128.22,
128.55, 129.11, 137.70, 138.24, 142.63.
1-[(E)-3-Bromo-2-nitroprop-1-enyl]benzene (3a); Typical Pro-
cedure
To a stirred soln of (E)-2-nitro-3-phenylprop-2-en-1-ol (2a, (0.72 g,
4 mmol) in CH2Cl2 (15 mL), 48% aq HBr (0.68 mL) was added at
r.t.. The mixture was cooled to 0 °C and then concd H2SO4 (0.05
mL) was added dropwise. The mixture was stirred well at r.t. for
about 24 h. On completion of the reaction (TLC analysis), the mix-
ture was poured into H2O and the aqueous layer was extracted with
EtOAc (3 × 10mL). The combined organic layers were washed with
brine (10 mL) and concentrated. The crude product thus obtained
was purified by column chromatography (EtOAc–hexanes) to pro-
vide 3a (0.60 g, 62%) as a yellow crystalline solid; mp 76–78 °C.
MS: m/z = 270 (M+), 271 (M+ + 1).
Anal. Calcd for C11H12BrNO2: C, 48.91; H, 4.48; N, 5.19. Found: C,
48.98; H, 4.56; N, 5.24.
1-[(E)-3-Bromo-2-nitroprop-1-enyl]-4-isopropylbenzene (3f)
Yield: 0.91 g (80%); mp 118–120 °C.
IR (KBr): 1637, 1538, 1353 cm–1.
1H NMR (300 MHz, CDCl3): d = 1.29 (d, J = 6.9 Hz, 6 H), 2.99
IR (KBr): 1635, 1518, 1323 cm–1.
1H NMR (300 MHz, CDCl3): d = 4.54 (s, 2 H), 7.44–7.54 (m, 5 H),
8.15 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 23.26, 129.48, 130.30, 131.20,
131.36, 137.43, 146.85.
MS: m/z = 242 (M+), 243 (M+ + 1).
(sep, J = 6.9 Hz, 1 H), 4.66 (s, 2 H), 7.39–7.59 (m, 4 H), 8.23 (s, 1
H).
13C NMR (75 MHz, CDCl3): d = 23.65, 34.25, 127.70, 128.67,
130.81, 137.72, 145.97, 153.16.
MS: m/z = 284 (M+), 285 (M+ + 1).
Anal. Calcd for C12H14BrNO2: C, 50.72; H, 4.97; N, 4.93. Found: C,
50.75; H, 4.95; N, 4.98.
Anal. Calcd for C9H8BrNO2: C, 44.66; H, 3.33; N, 5.79. Found: C,
44.72; H, 3.40; N, 5.83.
1-[(E)-3-Bromo-2-nitroprop-1-enyl]-2-methoxybenzene (3g)
Yield: 0.98 g (90%); mp 108–110 °C.
IR (KBr): 1647, 1537, 1342 cm–1.
1H NMR (300 MHz, CDCl3): d = 3.90 (s, 3 H), 4.61 (s, 2 H), 6.96–
7.68 (m, 4 H), 8.50 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 23.87, 55.74, 111.10, 120.43,
121.14, 129.63, 133.15, 133.57, 146.37, 158.75.
2-[(E)-3-Bromo-2-nitroprop-1-enyl]naphthalene (3b)
Yield: 0.93 g (80%); mp 118–120 °C.
IR (KBr): 1639, 1548, 1327 cm–1.
1H NMR (300 MHz, CDCl3): d = 4.58 (s, 2 H), 7.61–8.03 (m, 7 H),
8.84 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 22.25, 122.64, 124.41, 125.99,
126.60, 127.46, 127.96, 130.49, 130.59, 132.42, 134.43, 147.13.
MS: m/z = 272 (M+), 273 (M+ + 1).
MS: m/z = 292 (M+), 293 (M+ + 1).
Anal. Calcd for C10H10BrNO3: C, 44.14; H, 3.70; N, 5.15. Found: C,
44.20; H, 3.68; N, 5.23.
Anal. Calcd for C13H10BrNO2: C, 53.45; H, 3.45; N, 4.79. Found: C,
53.49; H, 3.41; N, 4.85.
1-[(E)-3-Bromo-2-nitroprop-1-enyl]-4-methoxybenzene (3h)
Yield: 1 g (92%); mp 102–104 °C.
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IR (KBr): 1638, 1535, 1363 cm–1.
1H NMR (300 MHz, CDCl3): d = 3.90 (s, 3 H), 4.68 (s, 2 H), 7.04–
7.65 (m, 4 H), 8.23 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 24.09, 55.59, 115.14, 123.46,
133.06, 137.72, 144.47, 162.44.
1H NMR (300 MHz, CDCl3): d = 4.96 (s, 2 H), 6.66–7.96 (m, 3 H),
8.00 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 23.04, 113.71, 122.82, 123.02,
143.13, 146.93, 148.41.
MS: m/z = 232 (M+), 233 (M+ + 1).
MS: m/z = 272 (M+), 273 (M+ + 1).
Anal. Calcd for C7H6BrNO3: C, 36.23; H, 2.61; N, 6.04. Found: C,
36.29; H, 2.70; N, 6.08.
Anal. Calcd for C10H10BrNO3: C, 44.14; H, 3.70; N, 5.15. Found: C,
44.18; H, 3.68; N, 5.20.
2-[(E)-3-Bromo-2-nitroprop-1-enyl]thiophene (3n)
Yield: 0.92 g (93%); mp 96–98 °C.
IR (KBr): 1639, 1517, 1328 cm–1.
4-[(E)-3-Bromo-2-nitroprop-1-enyl]-1,2-dimethoxybenzene (3i)
Yield: 1.1 g (92%); mp 130–132 °C.
IR (KBr): 1638, 1516, 1327 cm–1.
1H NMR (300 MHz, CDCl3): d = 3.92 (s, 6 H), 4.71 (s, 2 H), 7.01–
7.30 (m, 3 H), 8.23 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 24.35, 56.13, 56.15, 111.61,
112.75, 123.77, 125.83, 138.17, 144.52, 149.60, 152.12.
1H NMR (300 MHz, CDCl3): d = 4.81 (s, 2 H), 7.26–7.84 (m, 3 H),
8.41 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 23.05, 128.97, 130.59, 133.57,
135.03, 136.88, 143.32.
MS: m/z = 248 (M+), 249 (M+ + 1).
MS: m/z = 302 (M+), 303 (M+ + 1).
Anal. Calcd for C7H6BrNO2S: C, 33.89; H, 2.44; N, 5.65. Found: C,
33.91; H, 2.48; N, 5.62.
Anal. Calcd for C11H12BrNO4: C, 43.73; H, 4.00; N, 4.64. Found: C,
43.75; H, 4.03; N, 4.68.
1-[(E)-3-Chloro-2-nitroprop-1-enyl]benzene (4a); Typical Pro-
cedure
1-[(E)-3-Bromo-2-nitroprop-1-enyl]-4-fluorobenzene (3j)
To a stirred soln of (E)-2-nitro-3-phenylprop-2-en-1-ol (2a, 0.36 g,
2 mmol) in CH2Cl2 (10 mL), FeCl3 (0.48 g, 3 mmol) was added and
the mixture was stirred well at r.t. for about 6 h. On completion of
the reaction (TLC analysis), the mixture was poured into H2O and
the aqueous layer was extracted with EtOAc (3 × 10 mL). The com-
bined organic layers were washed with brine (10 mL) and concen-
trated. The crude product thus obtained was purified by column
chromatography (EtOAc–hexanes) to afford pure 4a ( 0.29 g, 73%)
as a white-colored solid; mp 118–120 °C.
Yield: 0.83 g (80%); mp 120–122 °C.
IR (KBr): 1637, 1526, 1325 cm–1.
1H NMR (300 MHz, CDCl3): d = 4.61 (s, 2 H), 7.21–7.68 (m, 4 H),
8.25 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 23.05, 116.15, 117.04, 132.67,
132.79, 136.31, 162.59, 165.96
MS: m/z = 260 (M+), 261 (M+ + 1).
IR (KBr): 1637, 1519, 1328 cm–1.
1H NMR (300 MHz, CDCl3): d = 4.79 (s, 2 H), 7.45–7.59 (m, 5 H),
8.28 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 61.65, 129.15, 130.24, 131.10,
131.38, 138.99, 147.36.
MS: m/z = 197 (M+), 199 (M+ + 2).
Anal. Calcd for C9H7BrFNO2: C, 41.57; H, 2.71; N, 5.39. Found: C,
41.60; H, 2.68; N, 5.43.
1-[(E)-3-Bromo-2-nitroprop-1-enyl]-2-chlorobenzene (3k)
Yield: 0.84 g (76%); mp 96–98 °C.
IR (KBr): 1643, 1538, 1327 cm–1.
1H NMR (300 MHz, CDCl3): d = 4.51 (s, 2 H), 7.44–7.74 (m, 4 H),
8.38 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 22.63, 127.57, 129.62, 130.17,
130.32, 132.12, 134.04, 135.48, 148.21.
Anal. Calcd for C9H8ClNO2: C, 54.70; H, 4.08; N, 7.09. Found: C,
54.61; H, 4.04; N, 7.13.
2-[(E)-3-Chloro-2-nitroprop-1-enyl]naphthalene (4b)
Yield: 0.37 g (74%); mp 98 °C.
MS: m/z = 276 (M+), 277 (M+ + 1).
IR (KBr): 1647, 1559, 1388 cm–1.
1H NMR (300 MHz, CDCl3): d = 4.61 (s, 2 H), 7.26–8.13 (m, 7 H),
8.89 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 61.67, 122.69, 124.45, 126.15,
126.63, 127.48, 127.98, 130.52, 130.62, 132.48, 135.47, 147.23.
MS: m/z = 247 (M+), 249 (M+ + 2).
Anal. Calcd for C9H7BrClNO2: C, 39.09; H, 2.55; N, 5.07. Found:
C, 39.10; H, 2.59; N, 5.10.
1-[(E)-3-Bromo-2-nitroprop-1-enyl]-3-chlorobenzene (3l)
Yield: 0.86 g (78%); mp 98–100 °C.
IR (KBr): 1639, 1517, 1325 cm–1.
1H NMR (300 MHz, CDCl3): d = 4.51 (s, 2 H), 7.33–7.71 (m, 4 H),
8.37 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 22.69, 127.59, 129.63, 130.15,
130.33, 132.16, 134.07, 135.48, 148.17.
Anal. Calcd for C13H10ClNO2: C, 63.04; H, 4.07; N, 5.66. Found: C,
63.10; H, 4.09; N, 5.70.
1-[(E)-3-Chloro-2-nitroprop-1-enyl]-2-methylbenzene (4c)
Yield: 0.36 g (85%); mp 142–144 °C.
MS: m/z = 276 (M+), 277 (M+ + 1).
IR (KBr): 1667, 1529, 1322 cm–1.
1H NMR (300 MHz, CDCl3): d = 2.14 (s, 3 H), 4.79 (s, 2 H), 7.45–
7.59 (m, 4 H), 8.28 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 20.05, 61.55, 126.43, 129.22,
130.52, 130.67, 130.78, 137.48, 138.16, 147.76.
MS: m/z = 211 (M+), 213 (M+ + 2).
Anal. Calcd for C9H7BrClNO2: C, 39.09; H, 2.55; N, 5.07. Found:
C, 39.10; H, 2.58; N, 5.04.
2-[(E)-3-Bromo-2-nitroprop-1-enyl]furan (3m)
Yield: 0.84 g (90%); mp 94–96 °C.
IR (KBr): 1623, 1528, 1335 cm–1.
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Synthesis of Bromo and Chloro Derivatives of Baylis–Hillman Adducts
617
Anal. Calcd for C10H10ClNO2: C, 56.75; H, 4.76; N, 6.62. Found: C,
56.73; H, 4.78; N, 6.58.
1H NMR (300 MHz, CDCl3): d = 3.91 (s, 2 H), 7.26–7.75 (m, 5 H),
8.27 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 49.47, 129.07, 130.45, 131.03,
1-[(E)-3-Chloro-2-nitroprop-1-enyl]-4-methylbenzene (4d)
Yield: 0.35 g (84%); mp 98 °C.
IR (KBr): 1632, 1549, 1338 cm–1.
1H NMR (300 MHz, CDCl3): d = 2.23 (s, 3 H), 4.75 (s, 2 H), 7.42–
7.56 (m, 4 H), 8.26 (s, 1 H).
131.22, 138.87, 147.16.
MS: m/z = 500 (M+).
Anal. Calcd for C27H24N4O6: C, 64.79; H, 4.83; N, 11.19. Found: C,
64.80; H, 4.85; N, 11.20.
13C NMR (75 MHz, CDCl3): d = 21.68, 61.62, 129.25, 130.27,
131.15, 131.37, 138.95, 147.33.
Tris[(E)-3-(naphthalen-2-yl)-2-nitroallyl]amine (5b)
Yield: 0.79 g (61%); mp 208–210 °C.
MS: m/z = 211 (M+), 213 (M+ + 2).
IR (KBr): 1628, 1510, 1325 cm–1.
Anal. Calcd for C10H10ClNO2: C, 56.75; H, 4.76; N, 6.62. Found: C,
56.72; H, 4.80; N, 6.60.
1H NMR (300 MHz, CDCl3): d = 3.41 (s, 2 H), 7.10–7.90 (m, 7 H),
8.68 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 48.53, 123.85, 125.26, 126.67,
127.21, 127.71, 128.55, 128.72, 130.71, 131.22, 133.29, 136.98,
148.70.
1-[(E)-3-Chloro-2-nitroprop-1-enyl]-4-ethylbenzene (4e)
Yield: 0.35 g (78%); mp 70–72 °C.
IR (KBr): 1631, 1549, 1318 cm–1.
1H NMR (300 MHz, CDCl3): d = 1.28 (t, J = 7.5 Hz, 3 H), 2.73 (q,
J = 7.5 Hz, 2 H), 4.76 (s, 2 H), 7.26–7.82 (m, 4 H), 8.28 (s, 1 H).
MS: m/z = 650 (M+).
Anal. Calcd for C39H30N4O6: C, 71.99; H, 4.65; N, 8.61. Found: C,
71.96; H, 4.67; N, 8.59.
13C NMR (75 MHz, CDCl3): d = 15.18, 21.92, 37.39, 128.39,
129.06, 130.65, 138.67, 145.67, 148.68.
Tris[(E)-2-nitro-3-(2-tolyl)allyl]amine(5c)
Yield: 0.81 g (75%); mp 212–214 °C.
IR (KBr): 1638, 1510, 1327 cm–1.
1H NMR (300 MHz, CDCl3): d = 2.19 (s, 3 H), 3.51 (s, 2 H), 7.14–
7.33 (m, 4 H), 8.33 (s, 1 H).
MS: m/z = 225 (M+), 227 (M+ + 2).
Anal. Calcd for C11H12ClNO2: C, 58.54; H, 5.36; N, 6.21. Found: C,
58.58; H, 5.40; N, 6.18.
1-Chloro-3-[(E)-3-chloro-2-nitroprop-1-enyl]benzene (4l)
Yield: 0.38 g (82%); mp 98 °C.
IR (KBr): 1641, 1529, 1327 cm–1.
1H NMR (300 MHz, CDCl3): d = 4.71 (s, 2 H), 7.49–7.81 (m, 4 H),
8.42 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 61.75, 127.63, 129.65, 130.17,
130.35, 132.19, 134.27, 135.43, 148.18.
13C NMR (75 MHz, CDCl3): d = 19.79, 48.39, 126.33, 129.20,
130.43, 130.56, 130.58, 137.40, 137.80, 147.69.
MS: m/z = 542 (M+).
Anal. Calcd for C30H30N4O6: C, 66.41; H, 5.57; N, 10.33. Found: C,
66.43; H, 5.60; N, 10.37.
Tris[(E)-2-nitro-3-(4-tolyl)allyl]amine(5d)
Yield: 0.80 g (74%); mp 205–207 °C.
IR (KBr): 1658, 1537, 1324 cm–1.
1H NMR (300 MHz, CDCl3): d = 2.37 (s, 3 H), 4.53 (s, 2 H), 7.29–
7.61 (m, 4 H), 8.35 (s, 1 H).
MS: m/z = 232 (M+), 234 (M+ + 2).
Anal. Calcd for C9H7Cl2NO2: C, 46.58; H, 3.04; N, 6.04. Found: C,
46.62; H, 3.08; N, 6.10.
2-[(E)-3-Chloro-2-nitroprop-1-enyl]thiophene (4n)
Yield: 0.32 g (80%); mp 138–140 °C.
IR (KBr): 1657, 1519, 1345 cm–1.
1H NMR (300 MHz, CDCl3): d = 4.93 (s, 2 H), 7.25–7.82 (m, 3 H),
8.45 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 36.06, 128.01, 130.32, 132.30,
133.80, 135.76, 142.00.
13C NMR (75 MHz, CDCl3): d = 20.01, 48.43, 126.70, 130.58,
131.00, 136.14, 138.61, 147.44.
MS: m/z = 542 (M+).
Anal. Calcd for C30H30N4O6: C, 66.41; H, 5.57; N, 10.33. Found: C,
66.38; H, 5.59; N, 10.36.
Tris[(E)-3-(4-ethylphenyl]-2-nitroallyl]amine (5e)
Yield: 0.85 g (62%); mp 140–142 °C.
IR (KBr): 1634, 1512, 1323 cm–1.
1H NMR (300 MHz, CDCl3): d = 1.20 (t, J = 7.5 Hz, 3 H), 2.62 (q,
J = 7.5 Hz, 2 H), 3.98 (s, 2 H), 7.07–7.47 (m, 4 H), 8.29 (s, 1 H).
MS: m/z = 203 (M+), 205 (M+ + 2).
Anal. Calcd for C7H6ClNO2S: C, 41.28; H, 2.97; N, 6.88. Found: C,
41.30; H, 2.95; N, 6.84.
Tris[(E)-2-nitro-3-phenylallyl]amine (5a); Typical Procedure
To a stirred soln of 1-[(E)-3-bromo-2-nitroprop-1-enyl)benzene
(3a, 0.48 g, 2 mmol) in MeOH (10 mL), NH4OAc (0.05 g, 0.66
mmol) was added and the mixture was stirred well at r.t. for 6 h. On
completion of the reaction (TLC analysis), MeOH was removed us-
ing a rotavapor. The mixture was poured into H2O and the aqueous
soln was extracted with EtOAc (3 × 10 mL). The combined organic
layers were dried (anhyd Na2SO4) and concentrated. The crude
product thus obtained was washed with Et2O to obtain pure 5a (0.80
g, 80%) as a yellow-colored solid; mp 155–157 °C.
13C NMR (75 MHz, CDCl3): d = 15.01, 28.77, 49.67, 128.59,
129.62, 131.01, 139.15, 146.27, 148.11.
MS: m/z = 584 (M+).
Anal. Calcd for C33H36N4O6: C, 67.79; H, 6.21; N, 9.58. Found: C,
67.80; H, 6.87; N, 9.60.
Tris[(E)-3-(2-methoxyphenyl)-2-nitroallyl]amine (5g)
Yield: 0.86 g (73%); mp 192–194 °C.
IR (KBr): 1638, 1517, 1323 cm–1.
1H NMR (300 MHz, CDCl3): d = 3.76 (s, 3 H), 3.79 (s, 2 H), 6.80–
7.47 (m, 4 H), 8.50 (s, 1 H).
IR (KBr): 1628, 1510, 1320 cm–1.
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13C NMR (75 MHz, CDCl3): d = 49.48, 55.51, 110.70, 120.50,
120.81, 130.78, 132.48, 134.88, 147.02, 158.11.
Acknowledgment
We thank CSIR and UGC (New Delhi) for the financial support. We
also thank DST-FIST for the NMR facility. N.S. thanks CSIR for
his SRF and A.D. thanks UGC for his fellowship.
MS: m/z = 590 (M+).
Anal. Calcd for C30H30N4O9: C, 61.01; H, 5.12; N, 9.49. Found: C,
61.00; H, 5.16; N, 9.53.
References
Tris[(E)-3-(4-methoxyphenyl)-2-nitroallyl]amine (5h)
Yield: 0.80 g (68%); mp 196–198 °C.
IR (KBr): 1635, 1517, 1321 cm–1.
(1) Basavaiah, D.; Reddy, B. S.; Badsara, B. S. Chem. Rev.
2010, 110, 5447.
(2) (a) Basavaiah, D.; Venkateswara Rao, K.; Reddy, R. J.
Chem. Soc. Rev. 2007, 36, 1581. (b) Basavaiah, D.; Rao, A.
J.; Satyanarayana, T. Chem. Rev. 2003, 103, 811.
(3) Ciganek, E. Org. React. 1997, 51, 201.
(4) (a) Aroyan, C. E.; Vasbinder, M. M.; Miller, S. J. Org. Lett.
2005, 7, 3849. (b) Kabalka, G. W.; Dong, G.; Venkataiah, B.
J. Org. Chem. 2005, 70, 9207. (c) Krafft, M. E.; Haxell, T.
F. N. J. Am. Chem. Soc. 2005, 127, 10168.
(5) (a) Basavaiah, D.; Aravindu, K. Org. Lett. 2007, 9, 2453.
(b) Basavaiah, D.; Mallikarjuna Reddy, R.;
Kumaragurubaran, N.; Sharada, D. S. Tetrahedron 2002, 58,
3693. (c) Shanmugam, P.; Viswambharan, B.; Madhavan, S.
Org. Lett. 2007, 9, 4095. (d) Deb, I.; Dadwal, M.; Mobin, S.
M.; Namboothiri, I. N. N. Org. Lett. 2006, 8, 1201.
(6) Gonzalez, A. G.; Silva, M. H.; Padron, J. I.; Leon, F.; Reyes,
E.; Alvarezmon, M.; Pivel, J. P.; Quintana, J.; Estevez, F.;
Bermejo, J. J. Med. Chem. 2002, 45, 2358.
(7) Mergott, D. J.; Frank, S. A.; Roush, W. R. Org. Lett. 2002,
4, 3157.
1H NMR (300 MHz, CDCl3): d = 3.76 (s, 3 H), 4.10 (s, 2 H), 6.65–
7.59 (m, 4 H), 8.34 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 50.02, 55.41, 114.63, 123.62,
133.42, 139.19, 144.74, 162.36.
MS: m/z = 590 (M+).
Anal. Calcd for C30H30N4O9: C, 61.01; H, 5.12; N, 9.49. Found: C,
61.06; H, 5.14; N, 9.54.
Tris[(E)-3-(3,4-dimethoxyphenyl)-2-nitroallyl]amine (5i)
Yield: 0.97 g (71%); mp 218–220 °C.
IR (KBr): 1637, 1524, 1326 cm–1.
1H NMR (300 MHz, CDCl3): d = 3.87 (s, 3 H), 3.89 (s, 3 H), 4.02
(s, 2 H), 6.67–6.92 (m, 3 H), 8.22 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 48.68, 56.17, 56.19, 111.65,
112.79, 123.92, 125.83, 138.19, 144.52, 149.60, 152.12.
MS: m/z = 680 (M+).
(8) Trost, B. M.; Thiel, O. R.; Tsui, H. C. J. Am. Chem. Soc.
2002, 124, 11616.
(9) Loh, T. P.; Cao, G. Q.; Pei, J. Tetrahedron Lett. 1998, 39,
1457.
Anal. Calcd for C33H36N4O12: C, 58.23; H, 5.33; N, 8.23. Found: C,
58.27; H, 5.20; N, 8.27.
Tris[(E)-3-(furan-2-yl)-2-nitroallyl]amine (5m)
Yield: 0.65 g (69%); mp 154–156 °C.
IR (KBr): 1627, 1523, 1325 cm–1.
1H NMR (300 MHz, CDCl3): d = 4.18 (s, 2 H), 6.54–7.64 (m, 3 H),
7.97 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 47.29, 111.04, 119.49, 121.44,
142.34, 145.06, 145.21.
(10) Basavaiah, D.; Bakthadoss, M.; Pandiaraju, S. A. Chem.
Commun. 1998, 1639.
(11) Buchholz, R.; Hoffmann, H. R. Helv. Chim. Acta 1991, 74,
1213.
(12) Masson, G.; Houssmann, C.; Zhu, J. Angew. Chem. Int. Ed.
2007, 46, 4614.
(13) Prasad, B. A. S.; Knochel, P. Tetrahedron 1997, 53, 16711.
(14) Huck, J.; Receveur, J. M.; Roumestant, M. L.; Martinez, J.
Synlett 2001, 1467.
MS: m/z = 470 (M+).
(15) Bakthadoss, M.; Murugan, G. Eur. J. Org. Chem. 2010,
Anal. Calcd for C21H18N4O9: C, 53.62; H, 3.86; N, 11.91. Found: C,
53.65; H, 3.81; N, 11.87.
5825.
(16) Bakthadoss, M.; Sivakumar, G.; Kannan, D. Org. Lett. 2009,
11, 4466.
(17) Bakthadoss, M.; Sivakumar, N. Synlett 2009, 1014.
(18) Bakthadoss, M.; Sivakumar, N.; Sivakumar, G.; Murugan,
G. Tetrahedron Lett. 2008, 49, 820.
Tris[(E)-2-nitro-3-(thiophen-2-yl)allyl]amine (5n)
Yield: 0.83 g (80%); mp 188–190 °C.
IR (KBr): 1632, 1527, 1325 cm–1.
1H NMR (300 MHz, CDCl3): d = 4.18 (s, 2 H), 7.10–7.63 (m, 3 H),
8.48 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 50.02, 128.34, 131.51, 132.95,
133.67, 136.96, 144.82.
(19) Bakthadoss, M.; Murugan, G. Synth. Commun. 2008, 38,
3406.
(20) Bakthadoss, M.; Murugan, G. Synth. Commun. 2009, 39,
1290.
(21) Rastogi, N.; Namboothiri, I. N. N.; Cojocaru, M.
Tetrahedron Lett. 2004, 45, 4745.
MS: m/z = 518 (M+).
Anal. Calcd for C21H18N4O6S3: C, 48.64; H, 3.50; N, 10.80. Found:
C, 48.72; H, 3.49; N, 10.67.
Synthesis 2011, No. 4, 611–618 © Thieme Stuttgart · New York