Impact of reaction dynamics on synthesis of novel nitrogen containing aldehydes

Article abstract of DOI:10.13005/ojc/290432

Impact of solvent dynamics, base employed and temperature conditions on the synthesis of novel Nitrogen containing aldehydes was studied. Piperazine, pyrrolidine and piperidine aldehydes were obtained in maximum yield and puritywith the K₂CO₃ base in presence of DMF solventand at 800 C temperatures.The synthesized compounds were characterized by IR, ¹HNMR and MS Spectroscopy.

Full text of DOI:10.13005/ojc/290432

ISSN: 0970-020 X
CODEN: OJCHEG
2013, Vol. 29, No. (4):
Pg. 1531-1534
ORIENTAL JOURNAL OF CHEMISTRY
An International Open Free Access, Peer Reviewed Research Journal
www.orientjchem.org
Impact of Reaction Dynamics on Synthesis
of Novel Nitrogen containing Aldehydes
RAJASHREE A. MARkANDEwAR1, HANFI M. ZIA2 and M. A. BASEER2
1Department of Applied Chemistry, Ballarpur Institute of Technology, Ballarpur - 442 701, India.
2Department of Chemistry, YeshwantMahavidyalaya, Nanded - 431 601, India.
http://dx.doi.org/10.13005/ojc/290432
(Received: September 09, 2013; Accepted: October 30, 2013)
ABSTRACT
Impact of solvent dynamics, base employed and temperature conditions on the synthesis of
novel Nitrogen containing aldehydes was studied.Piperazine, pyrrolidine and piperidine aldehydes
were obtained in maximum yield and puritywith the K2CO3 base in presence of DMF solventand
1
at 800 C temperatures.The synthesized compounds were characterized by IR, HNMR and MS
Spectroscopy.
key words: Nitrogen-containing-aldehyde, Reaction dynamics, N-arylation.
INTRODUCTION
compounds like anti depressant drug13-14 and
vasolidators15. Piperidine is also commonly used
in sequencing of DNA16 and in solid phase peptide
synthesis17.
Nitrogen containing compounds are used
as structural components of pharmaceuticals and
agrochemicals due to their high biological activities1.
There are many nitrogen containing chemicals,
rangingfromsimplestructuralcompoundsaspyridine
to complicated compounds as pharmaceutical
ingredients and their number is growing rapidly year
by year2.Pyrrolidine based compounds have wide
application in pharmaceutics ranging from use in
the treatment of cancer3,obesity4, fungal and viral
infections5, HIV infection6 and diabetes7-8.Piperazine
nucleus is one of the most important heterocycle,
exhibiting remarkable pharmacological activities
as anthelminitis9, anti- HIV agent, antanginals10,
urological11 and anticonvulsant compounds12.
Piperidine and its derivatives are ubiquitous
building blocks in the synthesis of pharmaceuticals
As per the review about recent trends in
chemistry of pyrrolidine, piperazine and piperidine
derivatives, their demand in pharmaceuticals is
increasing and still lies scope for the exploration of
pharmaco-kinetics of these compounds.
All these facts were driving force to
study the synthesis of 4(-4methyl piperazine-l-yl)
benzaldehyde, (4- pyrrolidin-l-yl) benzaldehyde
and (4-piperidine-l-yl) benzaldehyde.The present
work is concerned solely with the chemistry i.e. the
yield of the above mentioned products, for which
the dynamics of the environment (solvent, base and
temperature) can be responsible.

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MARKANDEwAR et al., Orient. J. Chem., Vol. 29(4), 1531-1534 (2013)
Study of different parameters on the synthesis
of aldehyde
ExpERIMENTAL
Incontinuationtoexplorethepharmaceutical
All the melting points were carried out in
significance of N-arylated moiety, thepiperazine, open capillary tubes and are uncorrected. The Thin
piperidine and pyrrolidinemoieties, it was planned Layer Chromatography was performed on precoated
to conduct a thorough study of the different silica plates and Iodine vapor is used for visualization.
parameters on the yield of 4-(4-methyl-piperazine- IR spectra were recorded in KBr disc on Shimadzu
1
l-yl) benzaldehyde, (4-pyrrolidine-l-yl) benzaldelyde FT-IR 8300 spectrophotometer. HNMR spectra
and (4-piperidine-l-yl) benzaldehyde.The systematic were recorded in DMSO-d6 on a Brucker Advance
studywascarriedoutkeepinginviewtheirsignificance II- 400 MHz Spectrometer using TMS as an internal
on the yield by virtue of effect of bases, solvents and standard.Mass spectra were recorded onVG7070H
temperature conditions as depicted in Table 1-3.
mass spectrometer.
Table 1: Effect of different bases
Synthesis of 4-(4-methyl piperazine-l-yl)
benzaldehyde[1a]
S. Name of
%Yield obtained
1b
In 4.0 ml of DMF, 1-methyl piperazine (0.1
gm. 0.001mol) was dissolved.To this solution K2CO3
(0.20gm, 0.00015 mol) was added and heated at
800C with stirring. After 30 min 4-flurobenzaldehyde
(0.124 gm, 0.001mol) was added and heating was
continued for 6 hours. On completion of reaction,
the reaction mixture was cooled and added drop
wise to ice-water.The separated product was filtered
and dried.The product obtained was pure and used
further without any purification.(M.P. 60-620C)
No Base Used
1a
1c
1. K2CO3
2. CsCO3
3. Na2CO3
4. KHCO3
5. NaHCO3
92%
88%
87%
85%
80%
94%
90%
84%
80%
76%
89%
80%
73%
60%
50%
Table 2: Effect of different solvents
S. Name of %Yield obtained
Table 3: Effect of different Temperature
No Base Used
1a
1b
1c
S. Name of
%Yield obtained
No Base Used
1a
1b
1c
1. DMF
95%
90%
70%
75%
No
96%
89%
65%
75%
No
90%
84%
62%
50%
No
2. DMSO
3. Toluene
4. Xylene
5. Methanol
1) 80-900C
2) 110-1200C
3) 150-1600C
92%
55%
Decom Decom
posed* posed*
86%
60%
90%
50%
Decom
posed*
reaction reaction reaction
No No No
reaction reaction reaction
6. Acetone
*- no of spots formed on TLC
Spectral Analysis
(t,4h,CH2); 3.3 (t,4H CH2); 7.2 (dd, 2H, aromatic) 8.1
(dd, 2H, aromatic) ; 9.9 (s, 1H, CHO)
IR:(cm-1): 1686 (C=O); 1561 (C=C).
1HNMR :.(DMSO) δppm : 2.0 (s,3H,CH3); 2.3 Mass: Mass (m/z): 204

MARKANDEwAR et al., Orient. J. Chem., Vol. 29(4), 1531-1534 (2013)
1533
Synthesis of (4-pyrrolidine-l-yl) benzaldehyde
[1b]
In 4.0 ml of DMF of pyrrolidine (0.1 gm,
0.001mol) was dissolved. To this solution K2CO3
(0.27 gm, 0.002mol) was added and heated at 800C
with stirring. After 30 min 4- fluorobenzaldehyde
(0.174 gm, 0.001 mol) was added and heating was
continued for six hours. On completion of reaction,
the reaction mixture was cooled and added dropwise
to ice water.The separated product was filtered and
dried. The product obtained was pure and used
further without any purification (M.P- 880 C)
Spectral Analysis
Synthesis of (4-piperidine-l-yl-) benzaldehyde
[1c]
In 4.0ml of DMF of piperidine (0.0gm,
0.001mol) was dissolved. To this solution K2CO3
(0.27gm, 0.002mol) was added and heated at 800C
with stirring. After 30 min 4-fluorobenzaldehyde
IR:(Cm-1) : 1653 (C=O); 1524 (C=C).
1HNMR :( DMSO) δppm: 2.2 (t,4H, CH2), 3.2 (t, 4H,
CH2), 6.4 (d, 2H,aromatic) 7.7.(d, 2H,aromatic), 9.8
(s, 1H CHO).
Mass: Mass (m/z) -175(M+ion)
(0.175 gm, 0.001mol) was added and heating was
continued for six hours. On completion of reaction,
the reaction mixture was cooled and added drop
wise to ice water.The separated product was filtered
and dried.The product obtained was pure and used
further without any purification. (M.P.-2890C)
such as CsCO3and Na2CO3 was less successful.
DMF was found to be the optimal solvent, although
the use of DMSO was also effective.
In conclusion, the synthesis of wide variety of
Nitrogen containing aldehydes is described with
proper choice of base, solvent and temperature
conditions. This work is underway to ameliorate
difficulties which remain, especially in finding
suitable reaction dynamics that efficiently increases
the yield.
Spectral Analysis
IR:(cm-1): 1651 (C=O), 1597 (C=C)
1HNMR (DMSO) δppm: 3.3 (t, 6H,CH2), 3.5
(t,4H,CH2),6.9 (d, 2H,aromatic), 7.6 (t,2H, aromatic)
,9.7 (s,1H,CHO).
ACkNOwLEDgEMENT
Mass: Mass (m/z): 189.
The authors are thankful to the Principal,
Yeshwant Mahavidyalaya, Nanded for providing lab
facilities and Director SAIF, Chandigarh for spectral
analysis.
CONCLUSION
Our studies showed that K2CO3 was the
most effective base, while the use of other bases
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