Ijaret 06 10_006

1. http://www.iaeme.com/IJARET/index.asp 27 editor@iaeme.com
International Journal of Advanced Research in Engineering and Technology
(IJARET)
Volume 6, Issue 10, Oct 2015, pp. 27-31, Article ID: IJARET_06_10_006
Available online at
http://www.iaeme.com/IJARET/issues.asp?JType=IJARET&VType=6&IType=10
ISSN Print: 0976-6480 and ISSN Online: 0976-6499
© IAEME Publication
___________________________________________________________________________
NEW SYNTHETIC STRATEGY FOR
SYNTHESIS OF NOVEL CLASS OF NITRO
OLEFIN DERIVATIVES
Nagappan Sivakumar and Chendrasekaran Yogalakshmi
Department Chemistry, AMET University Chennai 603 112, India
ABSTRACT
We have successfully synthesized a novel class (2E,2'E,2''E)-3,3',3''-
(4,4',4''-nitrilotris(benzene-4,1-diyl))tris(2-nitroprop-2-en-1-ol) and tris(4-
((Z)-2-nitrovinyl)phenyl)amine reaction for the first time. On the other hand
nitroolefins are very reactive species and have been widely utilized as Michael
acceptor. Interestingly, the nitroolefins are also utilized as dipolarophiles in
the [3+2] cycloaddition to prepare a wide variety of pyrrolidines.
Key words: Baylis-Hillman adducts paraformaldehyde imidazole and
anthranilic. (2E, 2’E, 2’’E)-3,3',3''-(4,4',4''-nitrilotris(benzene-4,1-diyl))tris(2-
nitroprop-2-en-1-ol) and tris(4-((Z)-2-nitrovinyl)phenyl)amine
Cite this Article: Nagappan Sivakumar and Chendrasekaran Yogalakshmi.
New Synthetic Strategy for Synthesis of Novel Class of Nitro Olefin
Derivatives. International Journal of Advanced Research in Engineering and
Technology, 6(10), 2015, pp. 27-31.
http://www.iaeme.com/IJARET/issues.asp?JType=IJARET&VType=6&IType=10
INTRODUCTION
Conjugate addition of carbon nucleophiles to electron- poor alkenes is of paramount
importance among the large body of synthetic processes devoted to carbon- carbon
bond formation.1-5
The first nucleophilic systems used for this purpose, more than a
century ago, were stabilized carbanions that can be prepared in polar solvents from
malonates and â-dicarbonyl derivatives in relatively mild conditions using bases of
moderate strength.2
This process is usually referred to as Michael addition, and ever
since the number of carbanionic species that have been used for conjugate additions
has considerably increased to include various enolate systems and strong nucleophilic
species such as organometallic reagents. The utilization of these carbon nucleophiles
has allowed the accomplishment of many synthetic processes with an outstanding
degree of selectivity even though the related experimental procedures are often
elaborated and not amenable to scale-up at the industrial level.pathways, thereby
making understanding the mechanism of this reaction an intellectual challenge6-10
.

2. Nagappan Sivakumar and Chendrasekaran Yogalakshmi
http://www.iaeme.com/IJARET/index.asp 28 editor@iaeme.com
Conjugate additions using highly stabilized carbanions are still of interest since a
growing number of these procedures can be carried out in environmentally benign
solvents such as water and using catalytic amounts of the basic promoter. In addition,
the achievement of diastereo- and enantioselective processes is no longer an exclusive
domain of highly reactive carbanionic systems working in carefully controlled
conditions3 but can be nowadays conducted even at room temperature using easily
available substrates and suitable base/solvent combinations.
Nitroalkanes are a valuable source of stabilized carbanions since the high
electron-withdrawing power of the nitro group provides an outstanding enhancement
of the hydrogen acidity at the R position (cf. pka MeNO2 ) 10).11-15
Nitronate anions 2
that can be generated from nitroalkanes 1 using a wide range of bases act as carbon
nucleophiles with common electrophiles including haloalkanes,9 aldehydes,16,17
and
Michael acceptors, leading to carbon-carbon bond formation The obtained adducts 3-
5 still retain the nitro function, and therefore, a suitable transformation of the nitro
group very often follows the main addition process. Reduction of the nitro group to a
primary amine 7 can be easily carried out providing a modification of the oxidation
state of the nitrogen atom
Alternatively, the nitro group can be removed from the molecule using two
distinct synthetic strategies. Replacement of the nitro group with hydrogen gives the
corresponding denitrated product 8 so that the whole process (nucleophilic addition-
denitration) closely resembles the addition of an organometallic reagent to an
electrophilic substrate.18
The presence at the â-position of an electron-withdrawing
group allows a base-assisted elimination of nitrous acid with consequent introduction
of a double bond in the molecular framework 9. A further option is represented by
conversion of the nitro group into a carbonyl group 10, a transformation widely
known as the Nef reaction, which ultimately leads to a reversal in the polarity of the
neighboring carbon atom from nucleophilic to electrophilic. This review is focused on
the utilization of nitroalkanes as nucleophiles in conjugate additions with electron-
poor alkenes and covers the new procedures and related applications appearing in the
literature after 1990. Emphasis will be given to asymmetric additions carried out
using optically active alkenes or with the aid of chiral catalysts.
GENERAL ASPECTS OF THE CONJUGATE ADDITION OF
NITROALKANES
Regioselectivity is an important feature that makes nitroalkanes particularly efficient
in conjugate additions with R,â-unsaturated carbonyl derivatives. Indeed, while other
activating groups such as phenylsulfonyl give variable amounts of 1,2-addition when
reacted with enones or enals,15 nitroalkanes afford exclusively 1,4-addition using
R,â-unsaturated ketones and propenal as reactive acceptors.16 Conversely, 3-
substituted R,â-unsaturated aldehydes give predominantly 1,2-addition with
secondary nitroalkanes and â-nitro alcohols.19,20
To execute our idea, first we have chosen the trialdehyde, nitro methane and
sodium hydride starting material for nitro olifen derivatives. The best results were
obtained when the addition of an trialdehyde and nitro methane presence sodium
hydride at 0o
C temperature and then acidified the reaction with hydrochloric acid to
form bulky white picepitate after filter successfully led to the desired producttris(4-
((Z)-2-nitrovinyl)phenyl)amine (3)
Encouraged by this result,we planned to synthesize Baylis-Hillman adducts (3) by
the treatment of tris(4-((Z)-2-nitrovinyl)phenyl)amine (3) with paraformaldehyde

3. New Synthetic Strategy For Synthesis of Novel Class of Nitro Olefin Derivatives
http://www.iaeme.com/IJARET/index.asp 29 editor@iaeme.com
using imidazole and anthranilic acid as catalytic system76
according to Scheme 1.
(2E,2'E,2''E)-3,3',3''-(4,4',4''-nitrilotris(benzene-4,1-diyl))tris(2-nitroprop-2-en-1-ol)
(4) in 75% yield after column chromatography purification. The compound 4 was
characterized by IR, 1
H & 13
C NMR spectroscopy, mass spectrometry and elemental
analysis
The 1
H NMR spectrum of compound 4 showed a singlet for hydroxyl proton at δ
2.51 and doublet was observed for O-CH2 protons at δ 4.65. The aromatic protons
appeared as multiplet in the region of δ 7.47-7.59. The olefinic proton observed as a
singlet at δ 8.27.
Scheme 1
The synthesis of nitrogen and oxygen containing heterocycles continues to be an
important and challenging area in the field of organic chemistry.59-62
The Baylis-
Hillman adducts and its derivatives are utilized as starting material for various organic
reactions which include several named reactions in organic chemistry. For instance,
recently the Baylis-Hillman adducts are utilized as dipolarophiles in [3+2]
cycloaddition chemistry.
CONCLUSION
In conclusion We have successfully synthesized a novel class (2E,2'E,2''E)-3,3',3''-
(4,4',4''-nitrilotris(benzene-4,1-diyl))tris(2-nitroprop-2-en-1-ol) and tris(4-((Z)-2-
nitrovinyl)phenyl)amine reaction for the first time. On the other hand nitroolefins are
very reactive species and have been widely utilized as Michael acceptor. Interestingly,
the nitroolefins are also utilized as dipolarophiles in the [3+2] cycloaddition to
prepare a wide

4. Nagappan Sivakumar and Chendrasekaran Yogalakshmi
http://www.iaeme.com/IJARET/index.asp 30 editor@iaeme.com
ACKNOWLEDGMENTS
We thank AMET University for the financial support. We also thank University of
Madras for the NMR facility. Indian institute of Technology, Chennai for IR, and
Mass Spectra.
Typical experimental procedure for the synthesis (2E,2'E,2''E)-3,3',3''-
(4,4',4''-nitrilotris(benzene-4,1 diyl))tris(2-nitroprop-2-en-1-ol) (4)
To a stirred solution of nitrostyrene (2) (1.40g, 10 mM) in THF (50 mL) at room
temperature was added imidazole (1.91g, 1 equiv) followed by anthranilic acid
(0.42g, 10 mo l %). Aqueous formaldehyde (38%, 60 mL, excess) was then added and
the reaction mixture was stirred at room temperature for 24 h. After completion of the
reaction (confirmed by TLC analysis), the reaction mixture was concentrated. Then
the reaction mixture was acidified with 5N HCl (20 mL) and the aqueous layer was
extracted with ethyl acetate (3x25 mL). The combined organic layers was washed
with brine (50 mL), dried over anhydrous Na2SO4 and concentrated in vacuo. The
residue was purified by silica gel column chromatography eluting with EtOAc–
hexanes (10%, gradient elution) to afford 172a Yellow oil in 53% (0.90g) yield.
IR (KBr): 3423, 1653, 1522, 1326, 1023, 695 cm-1
1
H NMR (CDCl3, 300 MHz): δ 2.61 (s, 1H), 4.65 (s, 2H), 7.47–7.59 (m, 5H), 8.22
(s, 1H). 13
C NMR (CDCl3, 75 MHz): 53.65, 129.19, 130.29, 130.91, 131.36, 137.87,
149.42.MS (m/z): 548 (M+
+1).Elemental Analysis for C27H24N4O9Calculated: C,
59.12; H, 4.41; N, 10.21. Found: C, 59.13; H, 4.40; N, 10.23.
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