Triphenylphosphine-iodine: An efficient reagent system for the synthesis of nitriles from aldoximes

Article abstract of DOI:10.1080/00397910500333225

A wide range of aldoximes were smoothly converted to the corresponding nitriles with triphenylphosphine-iodine. Copyright Taylor & Francis LLC.

Full text of DOI:10.1080/00397910500333225

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Triphenylphosphine–Iodine: An Efficient
Reagent System for the Synthesis of Nitriles
From Aldoximes
a
a
a
A. Venkat Narsaiah , D. Sreenu & K. Nagaiah
a
Division of Organic Chemistry, Fine Chemicals Laboratory, Indian Institute
of Chemical Technology, Hyderabad, India
Published online: 15 Aug 2006.
To cite this article: A. Venkat Narsaiah , D. Sreenu & K. Nagaiah (2006) Triphenylphosphine–Iodine:
An Efficient Reagent System for the Synthesis of Nitriles From Aldoximes, Synthetic Communications:
An International Journal for Rapid Communication of Synthetic Organic Chemistry, 36:2, 137-140, DOI:
10.1080/00397910500333225
To link to this article: http://dx.doi.org/10.1080/00397910500333225
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Synthetic Communications , 36: 137–140, 2006
Copyright # Taylor & Francis LLC
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910500333225
Triphenylphosphine–Iodine: An Efficient
Reagent System for the Synthesis of Nitriles
From Aldoximes
A. Venkat Narsaiah, D. Sreenu, and K. Nagaiah
Division of Organic Chemistry, Fine Chemicals Laboratory, Indian
Institute of Chemical Technology, Hyderabad, India
Abstract: A wide range of aldoximes were smoothly converted to the corresponding
nitriles with triphenylphosphine–iodine.
Keywords: Aldoximes, dehydration, iodine, nitriles, triphenlyphosphine
INTRODUCTION
Among the various methods available for the dehydration of aldoximes to
synthesize nitrites was found to be a convenient, mild, and efficient transform-
[1]
[2]
ation and many protocols were developed. As part of our ongoing
[3]
program directed at the development of efficient synthetic methodologies,
under mild reaction conditions, we report the conversion of aldoxime into
nitrile with TPP-I (Scheme 1).
2
In a typical procedure, treatment of 3,4,5-trimethoxybenzaldoxime (entry a)
with TPP-I in dichloromethane afforded 3,4,5-trimethoxybenzonitrile in 95%
2
yield. The reaction was completed in 3 h at room temperature. The versatility
of this methodology was examined with structurally diverse aldoximes
derived from aliphatic (entries c, l, k, o), aromatic (entries b, e, h, i, j, m,
n), and heterocyclic (entries d, f) precursors. In all cases, the reactions
Received in India July 14, 2005
IICT Communication No. 050106.
Address correspondence to K. Nagaiah, Division of Organic Chemistry, Fine
Chemicals Laboratory, Indian Institute of Chemical Technology, Hyderabad 500 007,
India. Fax: þ91-40-27160512; E-mail: nagaiah@iict.res.in
1
37

1
38
A. V. Narsaiah, D. Sreenu, and K. Nagaiah
Scheme 1.
proceeded efficiently. The dehydration of cinnamaldoxime (entry g) provided
a,b-unsaturated nitrile. The method was compatible with a wide range of
functional groups such as methoxy, methylenedioxy, phenoxy ethers, and
halogens present in the substrate. It appears that electron-withdrawing or
electron-donating groups had little effect on the rate of reaction. All the
1
products were characterized by H NMR, IR, and mass spectroscopy and
compared with literature reports.
[2]
The IR spectra were recorded on a Perkin-Elmer Infracord model 337.
NMR spectra were recorded on a Varian FT-200 MHz (Gemini) and
Table 1. TPP-I
2
–catalyzed synthesis of nitriles from aldoximes
Reaction
Yield
b
(%)
a
Entry
Substrate
Product
time (h)
a
3.0
95
b
c
4.0
5.0
3.5
92
89
91
d
e
f
4.5
4.0
5.0
93
84
86
g
h
4.0
91
(
continued)

Triphenylphosphine–Iodine
139
Table 1. Continued
i
4.5
93
j
5.0
6.0
6.0
89
85
87
k
l
m
n
3.5
90
4.0
5.0
88
86
o
a
1
[8]
All the products were confirmed by their IR, H NMR, and mass spectroscopy and
compared literature reports.
b
Yields were isolated and not optimized.
Brucker 300 MHz (Avance). Mass spectra were recorded on a Finnigan
Mat 1210 or Micro Mass 7070 spectrometer at 70 eV using a direct inlet
system.
GENERAL PROCEDURE
Triphenylphosphine (2 mmol) was added to a stirred mixture of aldoxime
(
2 mmol), in methylenedichloride (10 mL), followed by iodine (2 mmol).
The resulting mixture was stirred at room temperature for a specified period
Table 1). It was diluted with methylenedichloride (20 mL) and washed
(
with dilute sodium thiosulphate solution, followed by water and brine. The
organic layer was dried over Na SO , and the residue was purified on silica
gel by eluting with ethylacetate–n-hexane (1 : 9).
2
4
ACKNOWLEDGMENT
D. S. thanks Council of Scientific and Industrial Research (CSIR), New Delhi,
India, for the award of fellowship.

1
40
A. V. Narsaiah, D. Sreenu, and K. Nagaiah
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