Selective oxidation of arylaldoximes by cetyltrimethylammonium dichromate to arylaldehydes and arylnitriles

Article abstract of DOI:10.1080/00397910500282539

Aldoxime is converted into corresponding nitrile derivative on treatment with cetyltrimethylammonium dichromate. Copyright Taylor & Francis, Inc.

Full text of DOI:10.1080/00397910500282539

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Selective Oxidation of Arylaldoximes by
Cetyltrimethylammonium Dichromate to
Arylaldehydes and Arylnitriles
Sandhyamayee Sahu a , Sabita Patel a & Bijay K. Mishra a
a Centre of Studies in Surface Science and Technology, Department of
Chemistry , Sambalpur University , Jyoti Vihar, India
Published online: 20 Aug 2006.
To cite this article: Sandhyamayee Sahu , Sabita Patel & Bijay K. Mishra (2005) Selective Oxidation of
Arylaldoximes by Cetyltrimethylammonium Dichromate to Arylaldehydes and Arylnitriles, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 35:24,
3123-3126
To link to this article: http://dx.doi.org/10.1080/00397910500282539
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Synthetic Communicationsw, 35: 3123–3126, 2005
Copyright # Taylor & Francis, Inc.
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910500282539
Selective Oxidation of Arylaldoximes by
Cetyltrimethylammonium Dichromate to
Arylaldehydes and Arylnitriles
Sandhyamayee Sahu, Sabita Patel, and Bijay K. Mishra
Centre of Studies in Surface Science and Technology, Department of
Chemistry, Sambalpur University, Jyoti Vihar, India
Abstract: Aldoxime is converted into corresponding nitrile derivative on treatment
with cetyltrimethylammonium dichromate.
Keywords: Oxidation, arylaldoxime, cetyltrimethylammonium dichromate, arylnitrile
The conversion of oximes to nitriles have been carried out by using several
dehydrating agents like trifluoroacetic anhydride, chlorosulphonyl isocyanate,
diphosphorous tetraiodide, selenium dioxide, 4,6-diphenyl-2-methylthiopyry-
lium tetrafluoroborate, copper(II) acetate, and the triphenylphosphine/
CCl4.[1–4] Thionyl chloride has been used for conversion of oximes to nitriles
in benzotriazole mixture[5] and on silica surface.[6] Appropriate non metal
dehydrating agents have also been used for the conversion of nitriles from
amides and oximes.[7] Ruthenium catalyst in benzene has also been used as a
dehydrating agent during conversion of some sugar oximes and substituted
arylaldoxime to corresponding nitriles.[8] In a photoregeneration reaction of
carbonyl group from oxime, Lijser et al.[9] have obtained nitrile as a mixed product.
In continuation of our research in phase transferring oxidants[10,11] we
wish to report the reaction of cetyltrimethylammonium dichromate (CTADC)
with the oxime derivatives. For example, the oximes (1) on treatment with
CTADC in presence of trace amount of acetic acid in dichloromethane gave
Received in India June 24, 2005
Address correspondence to Bijay K. Mishra, Centre of Studies in Surface Science
and Technology, Department of Chemistry, Sambalpur University, Jyoti Vihar
768 019, India. E-mail: bijaym@hotmail.com
3123

3124
S. Sahu, S. Patel, and B. K. Mishra
the corresponding aldehydes (2) (Table 2). The colour change from orange to
green which suggested reduction of Cr(VI) to Cr(III). However, when the
above reaction was performed in the absence of acetic acid, the corresponding
nitrile derivatives (3) resulted (Table 1). The ketoximes remained unreacted
under these reaction conditions. The nitriles and aldehydes were identified by
comparison of melting/boiling points, IR and NMR spectral data with authentic
samples. The carbonyl compounds were also characterized from the melting
point of the 2,4-dinitrophenyl hydarazone derivatives and the IR spectral data.
EXPERIMENTAL
The melting point and boiling point of the compounds were obtained by
open capillary method. For the determination of boiling points of liquids
Siwoloboff’s method was used.[12] Oximes were prepared by standard
method.[13] These are characterized from the melting point and IR spectral
data. The IR spectra of the products were recorded on a Perkin Elmer RX-1
FTIR spectrometer in KBr disc for solids and in nujol for liquids. CTADC
was synthesised by method reported earlier.[10,11]
General Procedure for Oxidation of Oximes in Absence
of Acetic Acid (Representative Procedure for Dehydration
of p-Methoxybenzaldoxime)
A solution of CTADC (300 mg, 0.38 mmol) and p-methoxybenzaldoxime
(200 mg, 1.3 mmol) in CH2Cl2 (25 mL) was refluxed for 4 h and concentrated.
Table 1. Oxidation of oximes to corresponding nitriles by CTADC
Sl. no.
Oxime
Product
Mp (s)/bp (1)a Yield (%)
1
2
3
4
5
6
7
8
9
o-OMeC6H4CH55NOH o-OMeC6H4CN
p-OMeC6H4CH55NOH p-OMeC6H4CN
o-NO2C6H4CH55NOH o-NO2C6H4CN
p-NO2C6H4CH55NOH p-NO2C6H4CN
m-NO2C6H4CH55NOH m-NO2C6H4CN
137 (135)
60 (57)
70
85
72
86
90
80
90
78
84
106 (107)
144 (146)
117 (116)
43 (46)
o-ClC6H4CH55NOH
p-ClC6H4CH55NOH
o-OHC6H4CH55NOH
p-OHC6H4CH55NOH
o-ClC6H4CN
p-ClC6H4CN
o-OHC6H4CN
p-OHC6H4CN
89 (91)
92 (95)
110 (113)
a The values given in the parentheses are the literature values.[14]

Arylaldoximes Oxidation
3125

3126
S. Sahu, S. Patel, and B. K. Mishra
Ether was added to the residue, filtered and the filtrate evaporated to give
p-methoxybenzonitrile (yield 85%), m.p. 608C, lit.[14] m.p. 578C, IR (KBr)
n cm2l: 3392, 3102, 2223, 1605, 1509, 1257, 1175,1023, 829.
General Procedure for Oxidation of Oximes in the Presence
of Acetic Acid
A solution of CTADC (300 mg, 0.38 mmol), p-methoxybenzaldoxime
(200 mg, 1.3 mmol) and acetic acid (0.5 mL) in CH2Cl2 (25 mL) was
refluxed for 2 h and evaporated. The residue was then chromatographed on
silica gel by using chloroform as an eluent to give p-methoxybenzaldehyde
(yield, 90%) b.p. 2498C, m.p. of 2,4-dinitrophenylhydrazone, 2518C.[14]
ACKNOWLEDGMENT
The authors thank UGC and DST, New Delhi, India, for financial support
through DRS and FIST programs. S. P. thanks CSIR for JRF (NET).
REFERENCES
1. Mai, K.; Patil, G. Synthesis. 1986, 12, 1037.
2. Kim, S.; Yi, K. Y. Tetrahedron Lett. 1986, 27, 1925.
3. Lingaiah, N.; Narender, R. Synth. Commun. 2002, 32, 2391.
4. Kiasat, A. R.; Kazemi, F.; Khosravian, F. Phosphorus Sulfur Silicon Relat. Elem.
2003, 178, 1377.
5. Telvekar, V. N.; Akamanchi, K. G. Synth. Commun. 2004, 34, 2331.
6. Kazemi, F.; Kiasat, A. R.; Fadavipoor, E. Phosphoros Sulfur Silicon Relat. Elem.
2004, 179, 433.
7. Yang, S. H.; Chang, S. Org. Lett. 2001, 3, 4209.
8. Talukdar, A. Synth. Commun. 2002, 32, 3503.
9. de Lijser, H. J. P.; Fardoun, F. H.; Sawyer, J. R.; Quant, M. Org. Lett. 2002, 4,
2325.
10. Patel, S.; Kuanar, M.; Nayak, B. B.; Banichul, H.; Mishra, B. K. Synth. Commun.
2005, 35, 1033.
11. Patel, S.; Mishra, B. K. Tetrahedron Lett. 2004, 45, 1371.
12. Patel, S.; Panda, M. P.; Kuanar, M.; Mishra, B. K. Indian J. Chem. 2004, 43B,
1299.
13. Ahluwalia, V. K.; Dhingra, S. In Comprehensive Practical Organic Chemsitry,
Qualitative Analysis; University Press: Hyderabad, 2000; p. 54.
14. Aldrich Handbook of Fine Chemicals and Laboratory Equipment; Bangalore,
India, 2003–2004.