International Journal of Advanced Research in Engineering and Technology

(IJARET)
Volume 6, Issue 10, Oct 2015, pp. 32-35, Article ID: IJARET_06_10_007
Available online at
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ISSN Print: 0976-6480 and ISSN Online: 0976-6499
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SYNTHESIS OF TRIS (4-((E)-2-NITRO-3(PHENYLAMINO) PROP-1-ENYL) PHENYL)

AMINE DERIVED FROM BAYLIS
HILLMAN ADDUCT
Nagappan Sivakumar and Chendrasekaran Yogalakshmi
Department Chemistry, AMET University Chennai 603 112, India
ABSTRACT
In conclusion, we have successfully developed for the synthesis of bromo
and it is deriveties of BaylisHillman adducts derived from nitroolefins. This
novel class of bromo and amine 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 triallylamines which are core unit of dendrimers, thus
demonstrating 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.
Cite this Article: Nagappan Sivakumar and Chendrasekaran Yogalakshmi.
Synthesis of Tris (4-((E)-2-Nitro-3-(Phenylamino) Prop-1-Enyl) Phenyl)
Amine Derived From BaylisHillman Adduct. International Journal of
Advanced Research in Engineering and Technology, 6(10), 2015, pp. 32-35.
http://www.iaeme.com/IJARET/issues.asp?JType=IJARET&VType=6&IType=10

INTRODUCTION
The Morita-Baylis-Hillman reaction1 (MBH) is a base catalyzed carbon-carbon bond
formation process which involves electron-deficient alkenes and aldehydes.
Nucleophilic bases such as amines and phosphines2, 3 are necessary since the
commonly accepted mechanism4 involves an initial conjugate addition of the catalyst
to the activated alkene leading to a zwitterionic enolate, whose reaction with the
aldehyde is followed by a reversible elimination of the base to generate the product.
Different types of activated alkenes such as cyclic and acyclic, unsaturated ketones,
aldehydes, esters, amides, nitriles, and alkenes substituted by nitro groups, sulfoxides,
sulfones, sulfonic acids, or phosphonateand amine derivatives have been used in the
MBH reaction. Nitroalkenes are widely known as reactive electrophilic substrates
suitable for conjugate additions as well as cycloadditions reactions, but when involved
in Baylis-Hillman processes, these compounds can act as allyl-type nucleophiles.

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Synthesis of Tris (4-((E)-2-Nitro-3-(Phenylamino) Prop-1-Enyl) Phenyl) Amine Derived

From BaylisHillman Adduct

Reaction of nitroalkenes with bromomethyl acrylate in the presence of DBU affords

nitro dienes Conjugate addition of DBU to a nitroalkene gives a nitronate anion that in
the presence of acrylate reacts as previously described, leading to ammonium salt that
upon elimination of DBU affords nitro diene.1-5 (Hetero)aryl-R-nitro-R,-enals
(densely combine a (hetero)aromatic ring, a CdC double bond, a nitro group and a
formyl group to form an extended system, where three functionalities of
demonstrated utility in synthesis, namely, a (hetero) arylvinyl unit, an R,_-unsaturated
nitroalkene, and intimately coexist sharing a common double bond. Attractive as this
combination of structural and functional features could be, (hetero) aryl-R-nitro-R,_enals have nevertheless been essentially overlooked and their properties and synthetic
potential unexplored.6-9
This idea, we decided to prepare the bromo compound derived from nitroolefins,
which will open new avenues for synthetic transformations.16-20In continuation of our
research interest in the field of BaylisHillman chemistry,1520 we planned to
synthesize tris(4-((E)-2-nitro-3-(phenylamino)prop-1-enyl)phenyl)amine.
To demonstrate our approach, we first selected tris (4-((E)-3-bromo-2-nitroprop1-enyl)phenyl)amine a bromo derivative of the BaylisHillman (BH) adduct obtained
via the reaction of benzaldehyde and nitromethan, as the starting material for the
generation of the required precursor (3) with a view to obtain the desired compound.
The best results were obtained when BH bromide 3 was treated with aniline in the
presence of K2CO3 in THF for 1 h at room temperature to provided successfully the
desired tris(4-((E)-3-bromo-2-nitroprop-1-enyl)phenyl)amine 4 in 95% yield after
work up followed by column chromatography.

Scheme 1

The 1H NMR spectrum of the compound 4 showed the CH2 protons as a singlet at
= 4.52 ppm, The amine proton appears as broad singlet at = 2.52 ppm, the olefinic
proton as a singlet at = 7.97 ppm, and the aromatic protons as multiplets in the
regionn of = 7.537.62ppm.

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Nagappan Sivakumar and Chendrasekaran Yogalakshmi

CONCLUSION
In conclusion, we have successfully developed for the synthesis of bromo and it is
deriveties of BaylisHillman adducts derived from nitroolefins. This novel class of
bromo and amine 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 triallylamines
which are core unit of dendrimers, thus demonstrating the synthetic utility of the
bromo derivatives of the BaylisHillman adducts. Hence this novel protocol opens
new opportunities for the preparation of libraries of wide variety of new molecules

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.

tris(4-((E)-2-nitro-3-(phenylamino)prop-1 enyl)phenyl)amine: (4)Typical

Procedure
To a stirred solution of tris(4-((E)-3-bromo-2-nitroprop-1-enyl)phenyl)amine 3,
(2.94g, 4 mmol) in THF (15 mL), aniline (2.03 mL) was added at r.t. The mixture
was stirred well at r.t. for about 2 h. On completion of the reaction (TLC analysis), the
mixture 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 (EtOAchexanes) to provide 4 (7.34g, 95%) yield.
IR (KBr): 3429, 1657, 1525, 1324, cm-1
1
H NMR (300 MHz, CDCl3): = 2.52 (bs, 1H) 4.52 (s, 2 H), 7.537.62 (m, 27 H),
8.23 (s, 1 H). 13C NMR (75 MHz, CDCl3): = 57.61, 110.14, 128.15, 130.24, 131.23,
131.46, 138.89, 144.51, 145.37, 147.62.
MS: m/z = 773 (M+). Elemental Analysis for C45H39N7O6 Calculated: C, 69.84; H,
5.08; N, 12.67; Found: C, 69.83; H, 5.07; N, 12.68.

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Synthesis of Tris (4-((E)-2-Nitro-3-(Phenylamino) Prop-1-Enyl) Phenyl) Amine Derived

From BaylisHillman Adduct

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