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CeriumII) Chloride a Highly Efficient Reagent for the Synthesis of a-Aminonitriles

CeriumII) Chloride a Highly Efficient Reagent for the Synthesis of a-Aminonitriles

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10/25/2012

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Cerium(III) Chloride: A Highly EfficientReagent for the Synthesis of 
a
-Aminonitriles
M. A. Pasha
Department of Studies in Chemistry, Bangalore University, Bangalore,India
H. M. Nanjundaswamy
Chemical Examination Section, Public Health Institute, Bangalore, India
V. P. Jayashankara
Department of Studies in Chemistry, Bangalore University, Bangalore,India
Abstract:
We report a highly efficient, one-pot, three-component condensation of carbonyl compounds, amines, and TMSCN in MeCN; the reaction is significantlypromoted by the catalytic amount of cerium(III) chloride at ambient temperature inexcellent yields without any adverse effect on the other substituents. The methodafforded an elegant alternative to the synthesis of 
a
-aminonitriles. The reactions arefast and clean, and the products obtained are of high purity.
Keywords:
amines,
a
-aminonitriles, carbonyl compounds, cerium(III) chloride,one-pot three-component condensation
INTRODUCTION
a
-Aminonitriles are useful intermediates in the synthesis of amino acids andnitrogen-containing heterocycles.
[1]
Among many other applications, they arereadily converted to diamines, which are of interest as ligands for platinum(II)
Received in India May 21, 2007Address correspondence to M. A. Pasha, Department of Studies in Chemistry,Bangalore University, Central College Campus, Bangalore 560 001, India. E-mail:m_af_pasha@yahoo.co.in
Synthetic Communications
w
, 37: 4371–4380, 2007Copyright
#
Taylor & Francis Group, LLCISSN 0039-7911 print
/
1532-2432 onlineDOI: 10.1080/00397910701578180
4371
 
complexes with potential antitumor properties.
[2]
Although several procedureshave been devised for the synthesis of 
a
-aminonitriles, the Strecker reactionprovides one of the most efficient methods. The classical Strecker reaction isgenerally carried out with alkali cyanides in aqueous solution, which has somelimitations; consequently several modifications of the Strecker reaction havebeen reported using a variety of cyanating agents such as tributyltin cyanide(Bu
3
SnCN),
a
-trimethylsiloxynitriles, and diethyl phosphorocyanides undervarious reaction conditions.
[3]
Trimethylsilylcyanide (TMSCN) is a cyanide ionsource that provides a promising and safer route to this class of reactions.
[4]
Recently, one-pot procedures for the synthesis of 
a
-aminonitriles fromcarbonyl compounds have been developed in the presence of a variety of catalysts such as InCl
3
,
[5]
BiCl
3
,
[6]
NiCl
2
,
[7]
CoCl
2
,
[8]
Sc(OTf)
3
,
[9]
Cd(II)salt,
[10]
Pt salt,
[11]
I
2
,
[12]
and montmorillonite KSF clay.
[13]
RESULTS AND DISCUSSION
In continuation of our research program on organic transformations employingeasily available and inexpensive reagents under mild conditions at shortdurations, recently we have synthesized some medicinally importantmolecules.
[14]
Because of the significance of 
a
-aminonitriles, herein we report aclean procedure for the synthesis of a variety of 
a
-aminonitriles under mildconditions using catalytic cerium(III) chloride. The reaction is efficient andproceeds at room temperature either by the addition of a primary or secondaryamine to a mixture of aldehyde
/
trimethylsilyl cyanide (TMSCN) or by theaddition of an aldehyde to a mixture of amine
/
TMSCN in acetonitrile in thepresence of a catalytic amount of cerium chloride to give a high yield of theproduct as shown in Scheme 1.We chose benzaldehyde, aniline, and TMSCN as a representative reactionperformed in the presence of catalytic CeCl
3
in various organic solvents (viz.,methanol,dichloromethane,dichloroethane,tetrahydrofuran,ethanol,andaceto-nitrile). The reaction proceeds smoothly at room temperature, giving the corre-sponding
a
-aminonitrile in high yield (95%). Among the solvents examined,acetonitrileemergedassuperiormediumthatgaveexcellentresults.Theconden-sationofdifferentaldehydesandamineswasperformedundertheseconditionstoget
a
-aminonitrileswithin1.25to1.5 h(exceptentry16).Thecourseofreactionwas monitored by thin-layer chromatography (TLC). All the products obtainedby this system (listed in Table 1) were characterized by their melting
Scheme 1.
M. A. Pasha, H. M. Nanjundaswamy, and V. P. Jayashankara4372
 
Table 1.
Facile preparation of 
a
-aminonitriles catalyzed by cerium chlorideEntry 1 2 3
a
Time(h)Yield(%)
b
1 C
6
H
5
CHO C
6
H
5
NH
2
1.25 952 C
6
H
5
CHO C
6
H
5
CH
2
NH
2
1.50 923 C
6
H
5
CHO 2-MeC
6
H
4
NH
2
1.25 944 4-OMeC
6
H
4
CHO C
6
H
5
NH
2
1.25 965 4-OMeC
6
H
4
CHO 2-MeC
6
H
4
NH
2
1.25 906 2-OEtC
6
H
4
CHO C
6
H
5
NH
2
1.25 947 2-OEtC
6
H
4
CHO 2-MeC
6
H
4
NH
2
1.25 90(
continued 
)
 C e i    um (  I  I  I   )   Cl    oi    d  e  3  3 

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