Synthesis and characterization of N-methyl and N-benzyl cinnamohydroxamic acids

Article abstract of DOI:10.14233/ajchem.2017.20348

N-methyl and N-benzyl cinnamohydroxamic acid was prepared by coupling reaction between N-methyl hydroxylamine and N-benzyl hydroxylamine with cinnamoyl chloride. The compounds were structurally characterized with ¹H NMR, IR and elemental analysis.

Full text of DOI:10.14233/ajchem.2017.20348

Asian Journal of Chemistry; Vol. 29, No. 4 (2017), 885-887
A
SIAN
J
OURNAL OF HEMISTRY
C
https://doi.org/10.14233/ajchem.2017.20348
Synthesis and Characterization of N-Methyl and N-Benzyl Cinnamohydroxamic Acids
1,*
2
3
SURENDRA K. RAJPUT , ANITA PATEL and KISHOR N. BAPAT
1Department of Chemistry, V.Y.T.P.G. Autonomous College, Durg-490 001, India
2Department of Chemistry, Government Nagarjuna Post Graduate College of Science, Raipur-492 002, India
3Additional Director, Directorate of Higher Education, Raipur, India
*Corresponding author: Fax: +91 788 2211688; E-mail: skchem4450@yahoo.com
Received: 14 October 2016;
Accepted: 27 December 2016;
Published online: 31 January 2017;
AJC-18266
N-methyl and N-benzyl cinnamohydroxamic acid was prepared by coupling reaction between N-methyl hydroxylamine and N-benzyl
hydroxylamine with cinnamoyl chloride. The compounds were structurally characterized with 1H NMR, IR and elemental analysis.
Keywords: Synthesis, Cinnamohydroxamic acid, Hydroxylamine.
Synthesis of N-methyl cinnamohydroxamic acid (1a):
N-Methyl hydroxylamine (0.1 mol) was coupled with an
ethereal solution (50 mL) of cinnamoyl chloride (0.1 mol) in
the presence of saturated aqueous solution of sodium carbonate
(0.1 mol) on the magnetic stirrer with external cooling, keep
0-5 °C tempe-rature constant reaction, and recrystallize with
methanol [23] (Fig. 1). Colorless shiny crystal N-methyl
cinnamohydroxamic acid was obtained.
Synthesis of N-benzyl cinnamohydroxamic acid (1b):
N-benzyl hydroxyl amine (0.1 mol) was coupled with ethereal
solution (50 mL) of cinnamoyl chloride (0.1 mol) in the presence
of saturated aqueous solution of sodium carbonate (0.1 mol)
on the magnetic stirrer. Keep the temperature below than 5 °C
during the reaction and recrystallize with chloroform and
petroleum ether white shining N-benzyl cinnamohydroxamic
acid (1b) was obtained [23] (Fig. 2).
INTRODUCTION
Hydroxamic acids are prepared commonly from esters or
acid chlorides or carboxylic acids. Hydroxamic acids can also
be synthesized from aldehydes via Angeli-Rimini reaction, a
well-known hydroxamic acid reaction is Lossen rearrangement
[1]. In this paper, N-methyl and N-benzyl cinnamohydroxamic
acids are synthesized by the acylation of acid chloride or acid
anhydride.
Cinnamohydroxamic acid and their derivatives are weak
acid than the carboxylic acids. Hyrdoxamic acids formed N-
acid or O-acids by the deprotonation of nitrogen or oxygen
[2]. Solubility is one of the most important physico-chemical
parameters which plays an important role in drug manufacturing
process on the basis of solubility of cinnamohydroxamic acids
(solute) in liquid solvent [3]. They are often used as pharma-
cological [4-14] and drug discovery process [15-22].
RESULTS AND DISCUSSION
EXPERIMENTAL
The physico-chemical and elemental analysis of N-methyl
(1a) and N-benzyl cinnamohydroxamic acid (1b) has been
reported in Table-1.
Cinnamoyl hydroxylamine was procured from Sigma
Aldrich. All the compounds were precoured from Merck and
of AR grade. Melting points were determined on a melting
point apparatus and also determined by Thiele’s tube using
liquid paraffin by open capillary method. 1HNMR spectrum
of the compounds were carried out using BrukerAdvance 400
MHz spectrometer at SAIF Panjab University, Chandigarh,
India. The solvent used was CDCl3 and DMSO. IR spectra
were recorded on a FTIR 390/2014/0514/290514, Department
of Chemistry, Gujarat University, Ahmedabad, India. The
spectrum was recorded using the KBr Pellets.
1H NMR: The proton magnetic spectra of N-methyl and
N-benzyl cinnamohydroxamic acid are investi-gated and result
is given in Table-2. The chemical shift due to protons attached
to nitrogen atom in N-methyl cinnamohydroxamic acid, is
observed at 2.51 δ and chemical shift due to proton attached
to –CH2 in N-benzyl cinnamohydroxamic acid. The sharp
singlet observed in the spectra of N-methyl and N-benzyl
cinnamohydroxamic acids due to six magnetically equivalent

886 Rajput et al.
Asian J. Chem.
Cl
C
H3C
CH
N
C
OH
Ethereal medium
Coupling
NH
C6H5C
CH
O
H3C
OH
C6H5
CH
CH
O
N-methyl hydroxyl amine
Cinnamoyl chloride
N-methyl cinnamo hydroxamic acid (1a)
Fig. 1. Synthesis of N-methyl cinnamo hydroxamic acid (1a)
+
–
N
OH
N
O
H2C
HC
Alcohol 70 %
Reflux 3 h
Ethereal/HgO
Reflux 3 h
2
CH2Cl
CH2
CH2
Nitrone
HCl Reflux 1 h
Cl
H2C
N
C
OH
Ethereal medium
Coupling
CH2NHOH
C6H5
CH
CH
C
O
Cinnamoyl chloride
C6H5
CH
CH
O
N-Benzyl hydroxylamne
N-benzyl cinnamo hydroxamic acid (1b
)
Fig. 2. Synthesis of N-benzyl cinnamo hydroxamic acid (1b)
TABLE-1
PHYSICO-CHEMICAL DATA OF COMPOUNDS 1a AND 1b
Elemental analysis (%):
Calcd. (Found)
m.p.
(°C)
Yield
(%)
Compound
Structure
m.f.
m.w.
C
H
N
H3C
N
C
OH
O
67.78
6.21
7.90
C10H11NO2
177.20
160
75
80
1a
CH
CH
(67.098) (4.985) (3.909)
H2C
CH
N
C
OH
O
75.86
5.96
5.52
C16H15NO2
253.30
84
1b
(72.026) (5.483) (4.672)
CH
TABLE-2
proton present in benzene ring. The ring current effect due to π
electrons causes deshielding of aromatic protons which result
the chemical shift at high value. The doublet N-methyl (6.43-
7.35 δ) and N-benzyl (6.65-7.41 δ) observed, compounds are
due to chemically distinct protons. The splitting is due to spin-
spin coupling, splitting takes place when the non-equivalent
proton is present.
1H NMR SIGNALS OF SYNTHESIZED N-METHYL CINNAMO
HYDROXAMIC ACID (1a) AND N-BENZYL CINNAMO-
HYDROXAMIC ACID (1b): DI METHYL SULPHOXIDE
Cinnamon
hydroxamic
acid
Chemical
shift (τ)
Signal
(cps)
Assigned
group
Multiplicity
339
–
3.39
–
Singlet
–
CH3-N-
O–H
In the IR spectra of N-methyl and N-benzyl cinnamo-
hydroxamic acids, four regions of strong absorption were
observed. The band due to O-H stretching occur between 3092-
3026 cm-1 as a broad peak ranging from strong intensity to
medium intensity. The absorption bands due to (OH) stretching
vibration when free are observed around 3830 cm-1 but in case
of hydrogen reported the shift in the wavelength of this band is
towards lower frequency. Absorption near 1820-1698 cm-1 in
N-methyl and N-benzyl cinnamohydroxamic acid examined
here the characteristic C=O stretching vibration is assigned in
the region 1740-1620 cm-1. The position of carbonyl stretching
frequency is much more influenced by molecular structure
and shifted to 1000 cm-1 frequency due to strong intramolecular
bonding. The appearence of spectra range between 1493-1447
cm-1 is assigned to C-N stretching vibration, while the position
665
768
6.65
7.68
Doublet
Singlet
=CH
CH=
1a
741
735
7.41
7.35
Doublet
Triplet
251
–
643
757
2.51
–
6.43
7.57
Singlet
–
Doublet
Singlet
-CH2
O–H
=CH
CH=
1b
734
7.34
Doublet

Vol. 29, No. 4 (2017)
Synthesis and Characterization of N-Methyl and N-Benzyl Cinnamohydroxamic Acids 887
of N-O stretching bands has been assigned in1098-1072 cm-1
region.
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IR of N-methyl cinnamohydroxamic acid (1a): (3092)
O-H streching, (1698) C-H streching, (1620) C=O streching,
(1574) C=C streching, (1447) C-N streching, (1402) C-H
streching, (1329) C-H bending, (1281) C-N streching
(unsymmatrically), (1069) N-H bending (out-of-plane), (977)
N-O streching, (860) C-C-C streching, (766) C-H rocking,
(738) C-H rocking, (682) C-H twisting.
IR of N-benzyl cinnamohydroxamic acid (1b): (3026)
O-H streching, (2826) C-H streching, (1685) C=O streching,
(1576) C=C streching, (1418) C-H streching, (1312) C-H
bending, (1283) C-N streching, (1220) C-N streching (un
symmetrically, ) (1098) N-H bending (out-of-plane), (1072)
N-O streching, (877) C-C-C streching, (847) C-H rocking,
(766) C-H rocking, (704) C-H twisting, (587) C-H twisting,
(540) C-C= , (482) C-N-C.
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N-Methyl and N-benzyl cinnamohydroxamic acids have
synthesized by the acylation of acid chlorides or acid anhydride
chemicals in a good yield (75-80 %). The HNMR and IR
studies confirmed the structure of synthesized N-methyl and
N-benzylcinnamohydroxamic acid.
1
ACKNOWLEDGEMENTS
The authors thanks Department of Chemistry, Govt.
Nagarjuna Post Graduation College of Science, Raipur, India,
Department of Chemistry, SAIF Panjab University Chandigargh,
India for 1H NMR analysis, Gujarat University,Ahmedabad, India
for IR Analysis and CHN Lab, Panjab University, Chandigarh,
India for elemental analysis.
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