Efficient cleavage of carbon-nitrogen double bonds under solvent free conditions

Article abstract of DOI:10.1081/SCC-120006468

The conversion of oximes, hydrazones and semicarbazones into the corresponding carbonyl compounds is obtained conveniently using (NH₄)2Cr₂O₇ in the presence of ZrCl₄ and wet SiO₂ under solvent free conditions.

Full text of DOI:10.1081/SCC-120006468

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EFFICIENT CLEAVAGE OF CARBON–NITROGEN DOUBLE
BONDS UNDER SOLVENT FREE CONDITIONS
F. Shirini a , M. A. Zolfigol b & A. Pourhabib a
a Department of Chemistry, College of Science, Guilan University, Rasht, Iran
b Department of Chemistry, College of Science, Bu-Ali Sina University, Hamadan, Iran
Version of record first published: 18 Oct 2011.
To cite this article: F. Shirini, M. A. Zolfigol & A. Pourhabib (2002): EFFICIENT CLEAVAGE OF CARBON–NITROGEN DOUBLE
BONDS UNDER SOLVENT FREE CONDITIONS, Synthetic Communications: An International Journal for Rapid Communication of
Synthetic Organic Chemistry, 32:18, 2837-2841
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SYNTHETIC COMMUNICATIONS
Vol. 32, No. 18, pp. 2837–2841, 2002
EFFICIENT CLEAVAGE OF CARBON–
NITROGEN DOUBLE BONDS UNDER
SOLVENT FREE CONDITIONS
F. Shirini,1, M. A. Zolfigol,2 and A. Pourhabib1
*
1Department of Chemistry, College of Science,
Guilan University, Rasht, Iran
2Department of Chemistry, College of Science,
Bu-Ali Sina University, Hamadan, Iran
ABSTRACT
The conversion of oximes, hydrazones and semicarbazones
into the corresponding carbonyl compounds is obtained con-
veniently using (NH4)2Cr2O7 in the presence of ZrCl4 and wet
SiO2 under solvent free conditions.
Regeneration of carbonyl compounds from stable and readily prepared
oximes, hydrazones and semicarbazones has received attention in recent
years.[1–4] Since oximes can be prepared from olefins,[5] esters,[6] nitriles,[6]
nitro compounds,[7,11–13] nitrites,[8] alcohols,[9] and primary aliphatic
amines,[10] the regeneration of carbonyl compounds from oximes provides an
alternative method for the preparation of aldehydes and ketones. However,
many of these methods of generating carbonyl compounds from oximes
involve reagents which are either expensive or not readily available.[14–22]
*Corresponding author.
2837
DOI: 10.1081/SCC-120006468
Copyright & 2002 by Marcel Dekker, Inc.
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2838
SHIRINI, ZOLFIGOL, AND POURHABIB
Table 1. Regeneration of Aldehydes and Ketones from Oximes, Hydrazones, and
Semicarbazones
Entry
Substrate
Time (min)
Producta
Yield(%)b
1
2
3
4-Chlorobenzaldoxime
Acetophenone oxime
4-Methylacetophenone
oxime
10
90
15
4-Chlorobenzaldehyde
Acetophenone
4-Methylacetophenone
80
82
80
4
5
6
Benzophenone oxime
3-Nitrobenzaldoxime
4-Phenylcyclohexanone
oxime
60
8
30
Benzophenone
3-Nitrobenzaldehyde
4-Phenylcyclohexanone
90
60
75
7
8
Cyclohexanone oxime
4-Methylbenzaldehyde
hydrazone
10
15
Cyclohexanone
4-Methylbenzaldehyde
85
90
9
10
11
12
13
14
15
16
17
18
19
20
21
4-Methoxybenzaldehyde
hydrazone
4-Chlorobenzaldehyde
hydrazone
4-Nitrobenzaldehyde
hydrazone
3-Nitrobenzaldehyde
hydrazone
4-Methylacetophenone
hydrazone
4-Phenylcyclohexanone
hydrazone
Benzaldehyde
phenylhydrazone
2-Hydroxybenzaldehyde
semicarbazone
4-Methoxybenzaldehyde
semicarbazone
20
15
20
25
35
40
40
12
16
35
45
65
15
4-Methoxybenzaldehyde
4-Chlorobenzaldehyde
4-Nitrobenzaldehyde
3-Nitrobenzaldehyde
4-Methylacetophenone
4-Phenylcyclohexanone
Benzaldehyde
85
87
92
90
95
89
65
43
70
88
90
85
80
2-Hydroxybenzaldehyde
4-Methoxybenzaldehyde
3-Nitrobenzaldehyde
Acetophenone
3-Nitrobenzaldehyde
semicarbazone
Acetophenone
semicarbazone
1-Naphthaldehyde
semicarbazone
Cyclohexanone
1-Naphthaldehyde
Cyclohexanone
semicarbazone
1
aAll products were characterized by IR and H-NMR spectra and by comparison
with authentic samples.
bIsolate yield.

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CLEAVAGE OF CARBON–NITROGEN DOUBLE BONDS
2839
Table 2. Comparison of Some of the Results Obtained from Ammonium
Dichromate in the Presence of ZrCl4 and Wet SiO2 (1) with Some of Those
Reported with Pyridinium Chlorochromate (2),[1] Methyl Ammonium Chlorochro-
mate Adsorbed on Alumina (3),[2] and Chlorotrimethylsilane–sodium Nitrate (4).[3]
Yield(%)
Entry
Substrate
Product
1
2
3
4
1
2
Benzophenone oxime
Benzaldehyde
Benzophenone
Benzaldehyde
90
65
55
65
61
–
–
–
Phenylhydrazone
Acetophenone
semicarbazone
3
Acetophenone
90
15
–
80
Little attention has been paid to the cleavage of carbon–nitrogen double
bonds of hydrazones and semicarbazones, and only a few reports are avail-
able dealing with the conversion of the derivatives into their corresponding
carbonyl compounds.[4,23,24]
In this communication we report that ammonium dichromate in the
presence of ZrCl4 and wet SiO2 is able to perform the cleavage of carbon–
nitrogen double bonds of oximes, hydrazones and semicarbazones under
solvent free conditions (Table 1). Our experiments show that oximes, hydra-
zones and semicarbazones are converted into their corresponding carbonyl
compounds from good to high yields. It should be noted that these deoxi-
mation, dehydrazonation and desemicarbazonation reactions did not pro-
ceed using either ammonium dichromate, ZrCl4 or wet SiO2 alone, even
after prolonged heating. In order to show the ability of this system we
have compared some of the results with some of those reported in the
literature (Table 2).
In summary, ammonium dichromate in the presence of ZrCl4 and wet
SiO2 can serve as an efficient reagent for the cleavage of carbon–nitrogen
double bonds of oximes, hydrazones and semicarbazones. The yields are
almost quantitative and the procedure is simple and convenient.
EXPERIMENTAL
General Procedure
Amixture of the substrate (1 mmol), ammonium dichromate (1 mmol),
ZrCl4 (4 mmol) and wet SiO2[(SiO2/H2O : 20% ww), 0.4 g] was heated in a

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2840
SHIRINI, ZOLFIGOL, AND POURHABIB
water-bath (80ꢀC) for the specified time (Table 1). The reaction was mon-
itored by TLC or GLC. After completion of the reaction, CH2Cl2 (5 mL)
was added to the mixture and the resultant mixture was filtered. Anhydrous
MgSO4 was added to the filtrate and filtered. Evaporation of the solvent,
being followed by column chromatography on silica gel, gave the corres-
ponding carbonyl compounds from good to high yields.
ACKNOWLEDGMENT
We thank Guilan University Research Council for partial support of
this work.
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CLEAVAGE OF CARBON–NITROGEN DOUBLE BONDS
2841
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Received in the UK July 5, 2001