Sonochemical synthesis-of-ketone-aldehyde-oximes

INTERNATIONAL JOURNAL OF ADVANCE RESEARCH, IJOAR .ORG
ISSN 2320-9178 1
IJOAR© 2014
http://www.ijoar.org
International Journal of Advance Research, IJOAR .org
Volume 2, Issue 4, April 2014, Online: ISSN 2320-9178
SONOCHEMICAL SYNTHESIS OF KETONE - ALDEHYDE OXIMES
*Jitendra Kadu, *Sagar Patil, Sachin Pawar, Kavita Darvekar and Yogesh Patil¥,
*Bharatiya Jain Sanghatana College of Arts, Commerce and Science,
Pune-411007
All India Shri Shivaji Memorial Society’s
Institute of information Technology,
Pune-411001
Abstract
In recent days the various techniques have been used in synthesis of organic, inorganic
compounds which are harmless to environment under the name Green chemistry. Ultrasound
irradiation is one of these widely used techniques in chemistry and elsewhere. This short
communication reports the comparative study of synthesis of oxime using ultrasonic irradiation and
traditional chemical method. Oximes are used as intermediates in the organic synthesis of anilide, also
selective protection and de-protection of carbonyl group during synthesis to prefer conversion of
desired functional group in to targeted product. Yield and kinetics of oxime preparation by routine
chemical method and ultrasonic irradiation method are compared in this report. Yields by ultrasound
technique are found to be higher as compared to the yield by routine synthetic method. Even the time
required for completion of reactions by ultrasonic irradiation method was found to be less than that of
by traditional chemical method. Moreover the exclusion of organic solvent as reaction medium was
achieved.
Keyword: Oxime, Ultrasound technique, Analysis
------------------------------------------------------------------------------------------------------------------------------------------
¥
Author for correspondence
E-Mail: ypp@rediffmail.com

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INTRODUCTION
In this short report, we try to communicate effective use of ultrasound technique to
synthesise oximes. Oximes are normally in use as intermediate compound during anilide
synthesis, protection and de-protection of carbonyl group for selective synthesis, to check the
purity of carbonyl compounds; it also can be used as insecticide and pesticide. Ultrasound
irradiation enables many chemical reactions to proceed, because ultrasound can produce
temperature as high as that on the surface of the Sun; and pressure as great as that at the bottom
of the ocean by the acoustic cavitation mechanism. Cavitation means the formation, the growth,
and the impulsive collapse of bubble. During cavitation bubble collapse gives intense local heat
(of the order of »50000
C), and pressures (of about 1000 atmospheres) and heating and cooling
rates above 1010 K/s (1, 2). The reaction carried under ultrasonic irradiations has higher rate of
reaction as it provides activation energy in a short time also the selectivity of reactions pertaining
to the functional groups can be altered (3-5). Many organic reactions are done in a short time by
ultrasonic irradiation. As reported by Srinivasan et al, the heck reaction is completed in a very
short time (1.5-3 h) at ambient temperature (30°C) using ultrasonic technique (6).
Apart from this organic synthesis related application, the ultrasound technique is in use in
various fields like homogenisation of fluids and cell disruption in biochemistry, to assist in
mechanical operations like drilling, grinding, cutting, welding along with the mechanical testing
of a hard material, and also for cleaning and drilling in dentistry (7, 8).
An Oxime is an organic compound containing the >C=NOH functional group.
Oximes are the derivatives of aldehyde and ketone (Scheme 1) and are highly crystalline.
Therefore trasformation of an organic compound into oxime is a very efficient method for
characterisation and purification of carbonyl compound. Oximes are not only useful for
protection, purification, and characterization of carbonyl compound but also they can serve as
intermediate for conversion of carbonyl compounds into nitro compounds, nitriles and amides (9,
10).
ULTRASOUND IN OXIME SYNTHESIS: A number of criteria like toxicity, cost of starting
material, reagent and solvent usage, energy requirement, yield and time required for the
completion of reaction are to be considered to set reaction conditions for a chemical
transformation. In green chemistry, during organic synthesis it is aimed to form product in short
time, with high yield, minimum possible utilization of energy and without use of toxic
chemicals.

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Organic synthesis by routine method requires more time for the completion of the reaction and
vigorous reaction conditions like high pressure, temperature, use of catalyst, toxic organic
solvent still yield are comparatively low, which ultimately increases the cost of reaction and
leaves adverse effect on environment. As alternative routes of synthesis, Mostafa Karimkoshteh
reports use of Fe3O4 nanoparticles as catalyst during solvent free synthesis of oximes from
carbonyl compounds (12). It is reported that the magnetic nanoparticles can be used effectively
for synthesis of oxime in short period under clean reaction conditions, easy work-up procedure,
along with suppression of any side product. Another unconventional approach for synthesis of
oximes is put by Lakhinath Saikia and the co-authors in terms of grindstone chemistry. They
have proved the effective use of Bi2O3 as catalyst to run the reaction in churned form of the
reactants in order to follow ecofriendly synthesis (13). Use of ultrasonic irradiation in organic
synthesis gives product of the reaction in very short time with higher yield compare to routine
synthetic method, also it do not require high temperature, pressure and can be carried out even
without using catalyst and using less toxic solvent too (14). Hence these are green method of
preparation of organic compounds.
Experimental
Materials: All the chemicals used in the oxime preparations are procured from Merck Chemicals
India Ltd Purity: 99.9% AR Grade. The synthesis was carried out pertaining to the following
conditions:
Molar Ratio: Basis: 1 gm of Benzophenone
Benzophenone (5.4mM), Acetophenone (8.3 mM), 4-Chlorobenzaldehyde (7.3mM)
Temperature: i) for chemical method 580
C
ii) for ultrasonic method 250
C
Synthesis of Oxime:
In traditional way, preparation of oximes is carried out by refluxing carbonyl
compounds with hydroxylamine hydrochloride solution and ethyl alcohol as solvent (Scheme 1),
it takes around 50-60 minutes for the completion of reaction, the yield of product ranges around
70-75%.
Scheme 1: Proposed reaction:
Preparation of same oximes was attempted using ultrasonic irradiation. For this no reaction
medium was required; hence ethanol was absent and the reaction was carried out using sonicator
(Scheme 2). The proposed reactions for synthesis of oxime with starting material Benzophenone
(1), Acetophenone (2), 4-Chloro benzaldehyde (3) by ultrasonic irradiation are as follows,

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Scheme 2: Proposed reactions
RESULTS AND DISCUSSION
It is found that the product by ultrasound technique was formed in less time (10-20 min), with
yield ranging from 75 to 85 % which were high as compared to traditional one. The reduction in
time required is obvious as the cavitation increases the local temperature and pressure
enormously. The conversion takes place rapidly; the elevated temperature further favours the
conversion of aldehyde and ketones to oximes at high pressures. Though the rate of conversion is
increasing the yield is not found to be increasing considerably. This might be due to the limited
reactivity of carbonyl groups.
As shown in the table -1, in benzophenone, presence of two phenyl groups increases the electron
density considerably at carbonyl group to affect the conversion adversely. That is why the
%yield for benzophenone as starting material is the least amongst three of the reactants under
study.
The -CH3 group in Acetophenone neither support nor interferes the conversion rate as its electron
donating capacity is less as compare to phenyl group.
In 4-chlorobenzaldehyde, due to electron withdrawing effect of chlorine, reactivity of carbonyl
group is greater as compare to the group in other two reactants under study.
Time required for the completion of the reactions by ultrasonic irradiation was less as compared
to chemical method. Yield were also compared, it was found that yields of oxime prepared by
ultrasonic irradiation method were high as those of the chemical method.

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Table 1:- Comparative Results for Oxime preparation by Chemical and Ultrasonic
Method.
Sr.
No.
Name of
Compound
Results
Chemical method Ultrasound method
Melting
/
Boiling
point
o
C
Yield
%
Rf
Value
Time
in
min.
Melting
/ Boiling
point o
C
Yield
%
Rf
Value
Time
in
min.
1 Benzophenone
oxime
141 76.40 0.85 45 142 85 0.85 25
2 Acetophenone
oxime
60 78 0.70 40 60 89 0.70 20
3 4-Chloro
benzaldehyde
oxime
107 79 0.59 45 108 82.60 0.58 20
TLC: TLC (Thin layer chromatographic) plates were run using suitable mobile phase and same
chromatographic conditions for the identification of the product formed by routine chemical
synthetic method and ultrasonic method. Products formed by both the methods are found to
appear at same Rf value. Hence Oximes formed by both the method are identical is confirmed.
Fig a: TLC plates showing Benzophenone (1), oximes A (prepared by chemical method) and A-
1 (prepared by ultrasonic method)

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Fig b: TLC plates showing Acetophenone (2), oximes B (prepared by chemical method) and B-1
(prepared by ultrasonic method)
Fig c: TLC plates showing 4-chlorobezaldehyde (3), oximes C (prepared by chemical method)
and C-1 (prepared by ultrasonic method)
Infrared Data:
To confirm the formation of oximes by both the methods of preparation, the products obtained
were subjected for Infrared spectral analysis. The instrument used for the analysis was Bruker
FTIR with ATR in the region 4000-200 cm-1
.
The IR spectral values obtained for oximes prepared using three different starting materials are
tabulated as follow.
Table 2: C=N stretching frequencies of oximes (cm-1
) formed by chemical and ultrasonic
method
Sr.
No.
Name of Compound Results
Chemical method Ultrasound method Standard
1 Benzophenone oxime 1676 1660 1690 – 1620 cm-1
2 Acetophenone oxime 1644 1629 For oximes, the C=N
stretching band occurs in
the region 1690-1620 cm-1
.
[16].
3 4-Chloro
benzaldehyde oxime
1627 1639
Oximes have three characteristic bands in the infrared spectrum, at wavenumbers 3600 (O-H),
1665 (C=N) and 945 (N-O) (15). Oxime of benzophenone formed by chemical method (A)
shows C=N stretching frequencies at 1676.33 cm-1
and that of formed by ultrasonic irradiation
(A-1) shows C=N starching frequency at 1660.10 cm-1
which are within the standard range of
1650 – 1700 cm-1
.
The IR spectra for all the three oximes prepared by both chemical method and ultrasonic
irradiation method are given below,

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Fig d : IR Spectra for Oxime of Benzophenone(A) formed by chemical
method
Fig e : IR Spectra for Oxime of Benzophenone(A-1) formed by ultrasonic
method
Fig f : IR Spectra for Oxime of Acetophenone (B) formed by chemical
method
Fig g : IR Spectra for Oxime of Acetophenone(B-1) formed by ultrasonic method

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Fig h : IR Spectra for Oxime of 4-chlorobenzaldehyde (C) formed by chemical
method
Fig i : IR Spectra for Oxime of 4-chlorobenzaldehyde (C) formed by ultrasonic
method
CONCLUSION
The oximes can be synthesied by using ultrasound technique. The ultrasonic irradiation method
for the synthesis of organic compound is more efficient method as compare to routine organic
synthesis as it limits the use of toxic, volatile and carcinogenic organic solvent. Reaction can be
carried out at ambient temperature, which ultimately saves energy and achieves economy.
Chemical method is time consuming with low rate of reaction however the ultrasonic irradiation
method is having high rate of reaction. Hence it can be stated that ultrasound technique is in
favour of green synthesis of oximes starting with benzophenone, acetophenone and 4-
chlorobenzaldehyde. However the substituent at carbonyl group of starting material has
pronounced effect on its conversion rate to the oxime.

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