NH2OH.HCl/BaCl2: A convenient system for synthesis of oximes from the corresponding of organic carbonyl compounds

Article abstract of DOI:10.13005/ojc/320334

A variety of aldehydes and ketones were converted to their corresponding oximes NH₂OH·HCl/BaCl₂ system in reflux conditions.

Full text of DOI:10.13005/ojc/320334

ISSN: 0970-020 X
CODEN: OJCHEG
2016, Vol. 32, No. (3):
Pg. 1583-1587
ORIENTAL JOURNAL OF CHEMISTRY
An International Open Free Access, Peer Reviewed Research Journal
www.orientjchem.org
NH2OH.HCl/BaCl2: A Convenient System for Synthesis
of Oximes from the Corresponding of Organic Carbonyl
Compounds
FARHAd TALAEI and dAvOOd SETAMdIdEH*
Department of Chemistry, Mahabad Branch, Islamic Azad University, Mahabad, Iran.
*Corresponding author E-mail: davood.setamdideh@gmail.com
http://dx.doi.org/10.13005/ojc/320334
(Received: October 08, 2015; Accepted: November 17, 2015)
ABSTRACT
A variety of aldehydes and ketones were converted to their corresponding oximes NH2OH·HCl/
BaCl2 system in reflux conditions.
Keywords: Oximes, aldoximes, acetophenone oximes, H2NOH.HCl, BaCl2.
INTROdUCTION
RESULTS ANd dISCUSSIONS
Oximes have many applications in organic
synthesis1. These compounds have antimicrobial,
antioxidant, antitumor, anti-depressive, antiviral
agents, and anticonvulsant properties2-7. Some
oximation methods have been reported8. However
our ongoing attentions to the development of new
modified methods in organic synthesis8-15, we have
investigated the oximation of a variety of carbonyl
compounds with NH2OH·HCl in the presence of
BaCl2.
For finding optimization reaction conditions
bezaldehyde and acetophenone have been used
as model compounds. Experiments showed that
using NH2OH.HCl (1.2 mmol) and BaCl2 (1 mmol)
in C2H5OH (3 ml) was the best conditions for the
oximation of benzaldehyde. The reaction was
completed within 30 minutes in reflux conditions with
the excellent yield (95%) of the product as shown in
scheme 1.
Ph
Ph
NH2OH.HCl (1.2 mmol), BaCl2 (1 mmol)
NHOH
O
C2H5OH (3 ml), reflux, 30 min,
Conversion 100%
H
H
Scheme 1:

TAlAEI & SETAMDIDEH, Orient. J. Chem., Vol. 32(3), 1583-1587 (2016)
1584

TAlAEI & SETAMDIDEH, Orient. J. Chem., Vol. 32(3), 1583-1587 (2016)
1585
A variety of aldehydes were ground with
NH2OH·HCl/BaCl2 system under optimized reaction
conditions. In this approach, the corresponding
Z-aldoximes were obtained in quantitative yield
(93-98%).The results have been reported in table 1.
Then, the oximation of ketones was also performed
well by NH2OH·HCl/BaCl2 system. Experiments
showed the oximation of ketones requires higher
molar amounts of NH2OH·HCl (1.5 mmol) and BaCl2
(1 mmol) vs. 1 mmol of the substrates.The reaction
of acetophenone was completed in 65 minutes with
the excellent yield (93%) as shown in scheme 2.
Avarietyofacetophenonesweregroundwith
NH2OH·HCl/BaCl2 system under optimized reaction
conditions. In this approach, the corresponding
E-acetophenonoximes were obtained in quantitative
yield (87-95%). The results have been reported in
table 2.
Allsubstratesandreagentswerepurchased
from commercially sources with the best quality. IR
and 1H NMR spectra were recorded on PerkinElmer
FT-IR RXI and 300 MHz Bruker spectrometers,
respectively. The products were characterized by
1
their H NMR or IR spectra and comparison with
authentic samples (melting points).All yields referred
to isolated pure products.The purity of products was
1
determined by TlC and H NMR. Also, reactions
were monitored by TlCs utilizing plates cut from
silica gel 60 F254 aluminum sheets.
A typical procedure for the oximation with
NH2OH·HCl/BaCl2 system
In a round-bottomed flask (10 ml) equipped
with a condenser, a mixture of benzaldehyde (0.106
g, 1 mmol), NH2OH·HCl (0.084 g, 1.2 mmol) and
BaCl2 (0.2 g, 1 mmol) in ethanol (3 ml) was prepared.
The mixture was stirred under reflux conditions for 30
min.The progress of the reaction was monitored by
TlC. After completion of the reaction, H2O (10 ml)
was added and the reaction mixture was continued
to stirring for 5 min.The product has been extracted
with CH2Cl2 (3õ15 ml).The mixture was dried over
anhydrous Na2SO4. Evaporation of the solvent and
a short column chromatography of the resulting
crude material over silica gel (eluent;CCl4/Et2O:5/2)
afforded the pure benzaldoxime (0.115 g, 95 % yield,
table 1, entry 1).

1586
TAlAEI & SETAMDIDEH, Orient. J. Chem., Vol. 32(3), 1583-1587 (2016)

TAlAEI & SETAMDIDEH, Orient. J. Chem., Vol. 32(3), 1583-1587 (2016)
1587
Ph
Ph
NH2OH.HCl (1.5 mmol),BaCl2 (1 mmol)
O
NHOH
C2H5OH (3 ml), reflux, 65 min,
Conversion 100%
H3C
H3C
Scheme 2:
CONCLUSION
The oximation of a variety of aldehydes and
ketones was carried out efficiently with NH2OH·HCl/
BaCl2 system. The reactions were performed in
ethanol under reflux conditions. Excellent yields
(93-98%) of products in appropriate times (30-100
min) have been achievement.
ACKNOwLEdgEMENTS
The authors gratefully appreciated the
financial support of this work by Islamic Azad
University branch of Mahabad.
REFERENCES
1.
2.
Xia, J. J.; Wang, G. W. Molecules 2007, 12,
231-236.
li, H. Q.; Xiao, Z. P.; Yin, l.; Yan, T.; lv, P.C.;
Zhu , H. l. . Eur. J. Med. Chem. 2009, 44,
2246-2251.
Karakurt, A.; Sevim, D.; Özalp, M.; Özbey, S.;
Kendi, E.; Stables, J. P. Eur. J. Med. Chem.
2001, 36, 421-433.
Puntel, G. O.; de Carvalho, N. R.; Gubert,
P.; Palma, A. S.; Corte, C. l. D.; Ávila, D. S.;
Pereira, M. E.; Carratu, V. S.; Bresolin, l.; J.
Da Rocha, B. T.; Soares, F. A. A. Chem. Biol.
Interact. 2009, 177, 153-160.
Wang, T. C.; Chen, I. l.; lu, C. M.; Kuo, D. H.;
liao, C. H Chem. Biodivers. 2005, 2, 253-
263.
De Sousa, D. P.; Schefer, R. R.; Brocksom
U.; Brocksom, T. J. Molecules 2006, 11, 148-
155.
Hu, D.Y.; Zeng, S. Bioorg. Med. Chem. 2008,
16, 9699-9707.
8.
Setamdideh, D.;Khezri, B.;Esmaeilzadeh, S.
J. Chin. Chem. Soc. 2012, 59, 1119- 1124.
Setamdideh, D.; Khezri, B.; Alipouramjad, A.
J. Chin. Chem. Soc. 2013, 60, 590-596.
Sofighaderi, S.; Setamdideh, D. Orient. J.
Chem. 2013, 29, 1135-1137.
9.
3.
4.
10.
11.
12.
Setamdideh, D.; Sepehraddin, F. J. Mex.
Chem. Soc. 2014, 58, 22-26.
Azizi Asl, P.; Setamdideh, D. J. Chin. Chem.
Soc. 2014, 59, 940-944. f) Setamdideh, D. J.
Mex. Chem. Soc. 2014, 58, 230-234.
Azimzadeh, M.; Setamdideh, D. Orient. J.
Chem., 2015, 31, 1085-1089.
Rezaeekhoredehforosh, R.; Khezri, B.;
Setamdideh, D. Orient. J. Chem., 2015, 31,
1205-1209.
5.
6.
7.
13.
14.
15.
Mahmoudi, M.; Setamdideh, D. Orient. J.
Chem., 2015, 31, 1215-1218.
Ouyang, G.; Chen, Z.; Cai, X. J.; Song, B. A.;
Bhadury, P. S.; Yang, S.; Jin, l. H.; Xue, W.;