Efficient and Mild Regeneration of Carbonyl Compounds from Oximes and Hydrazones by Manganese(III) Porphyrin-Periodate

Article abstract of DOI:10.1039/a802186d

The periodate-manganese tetraphenylporphyrin, Mn(tpp)/1O₄^-, catalytic system is efficient in regenerating the parent carbonyl compounds from oximes and phenylhydrazones at room temperature.

Full text of DOI:10.1039/a802186d

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4
56 J. CHEM. RESEARCH (S), 1998
J. Chem. Research (S),
Efficient and Mild Regeneration of Carbonyl
Compounds from Oximes and Hydrazones by
Manganese(III) Porphyrin±Periodate$
1998, 456±457$
Shahram Tangestaninejad,* Mohammad Hossein Habibi and
Mohammad Reza Iravani
Department of Chemistry, Esfahan University, Esfahan 81744, Iran
4�
The periodate±manganese tetraphenylporphyrin, Mn(tpp)/IO , catalytic system is efficient in regenerating the parent
carbonyl compounds from oximes and phenylhydrazones at room temperature.
Oxidation reactions catalysed by metalloporphyrins,
especially iron-(III) and manganese(III) complexes, that
mimic cytochrome P-450 dependent monooxygenases, are
Most aromatic aldoximes and ketoximes were easily con-
verted into their corresponding aldehydes and ketones in
high yields within 1±3 h at room temperature (Table 1).
Further oxidation of aldehydes to their carboxylic acids
was not observed. Tetrabutylammonium periodate was
employed as an e€ective source of oxygen atom donor for
oxidative deoximation in the presence of catalytic amounts
of manganese tetraphenylporphyrin in a single phase system
at room temperature.
1
attracting continuing interest. The conversion of oximes
and hydrazones into the parent carbonyl compounds under
mild conditions is an important process in organic chem-
istry. A number of methods have been reported for the
2
±7
oxidative cleavage of oximes and phenylhydrazones,
which frequently necessitate relatively forceful reaction
conditions.
Recently we have introduced NaIO4 and Bu NIO4 as
Comparison of the two systems showed that Mn(tpp)Cl/
Bu NIO was milder than Mn(tpp)Cl/NaIO .
4 4 4
4
e€ective oxygen atom donors for the epoxidation of ole®ns,
We now
Phenylhydrazones and p-nitrophenylhydrazones are also
transformed to their carbonyl compounds by Mn(tpp)Cl/
8,9
catalysed by manganese tetraphenylporphyrin.
report the use of sodium periodate in the presence of
manganese(III) tetraphenylporphyrin for oxidative regener-
ation of carbonyl compounds from oximes and phenyl-
hydrazones in a two-phase system, CH Cl /H O, at room
NaIO
homogeneous Mn(tpp)Cl/Bu
4
system at room temperature (Table 2). However, the
NIO system was less ecient.
4
4
In the absence of manganese(III) tetraphenylporphyrin
catalyst, NaIO4 and Bu NIO4 were much less ecient in
2
2
2
4
temperature. As far as we know, this type of reaction is
novel in oxidation systems catalysed by metalloporphyrins.
regeneration of carbonyl compounds from oximes and
hydrazones at room temperature.
Table 1 Regeneration of aldehydes and ketones by Mn(tpp)Cl/NaIO
4
4 4
and Mn(tpp)Cl/Bu NIO systems
b
Yield (Time/h)
%
a
Run
Substrate
Product
Mn(tpp)Cl/NaIO
4
4 4
Mn(tpp)Cl/Bu NIO
1
2
3
4
5
6
7
Anisaldoxime
2,6-Dimethoxybenzaldoxime
Salicylaldoxime
Acetophenone oxime
Benzophenone oxime
9-Fluorenone oxime
p-Phenylacetophenone oxime
Anisaldehyde
90 (2)
85 (2)
60 (3)
80 (2.5)
85 (1)
83 (2)
85 (1)
94 (2.5)
90 (3.5)
60 (4)
82 (3.5)
88 (1.5)
86 (2.5)
92 (2)
2,6-Dimethoxybenzaldehyde
Salicyaldehyde
Acetophenone
Benzophenone
9-Fluorenone
p-Phenylacetophenone
a
b
All products were identified by comparison with authentic samples (IR, NMR, mp). Isolated yield.
Table 2 Regeneration of aldehydes and ketones from phenylhydrazones and p-nitrophenylhydrazones by Mn(tpp)Cl/NaIO
4
a
b
Run
Substrate
Product
Time (h)
Yield (%)
1
2
3
4
5
6
7
8
9
Anisaldehyde phenylhydrazone
Anisaldehyde
5
8
3.5
3
4
3
8
5
3
82
40
80
82
80
80
35
75
75
73
80
45
2-Nitrobenzaldehyde phenylhydrazone
Benzophenone phenylhydrazone
Acetophenone phenylhydrazone
2-Nitrobenzaldehyde
Benzophenone
Acetophenone
p-Chloroacetophenone
p-Phenylacetophenone
m-Nitrobenzaldehyde
Anisaldehyde
Acetophenone
Benzophenone
p-Phenylacetophenone
p-Chloroacetophenone
p-Chloroacetophenone phenylhydrazone
p-Phenylacetophenone phenylhydrazone
m-Nitrobenzaldehyde phenylhydrazone
c
Anisaldehyde 4-NPH
Acetophenone 4-NPH
1
1
1
0
1
2
Benzophenone 4-NPH
p-Phenylacetophenone 4-NPH
p-Chloroacetophenone 4-NPH
3.5
3
4
a
b
All products were identified by comparison with authentic samples (IR, NMR, mp). Isolated yield. 4-NPH stands for
c
4-nitrophenylhydrazone.
*
To receive any correspondence.
Experimental
All chemicals used were reagent grade. The tetraphenylporphyrin
was prepared and metallated according to the literature.
$This is a Short Paper as de®ned in the Instructions for Authors,
Section 5.0 [see J. Chem. Research (S), 1998, Issue 1]; there is there-
fore no corresponding material in J. Chem. Research (M).
10,11

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J. CHEM. RESEARCH (S), 1998 457
General Procedure for Regeneration of Carbonyl Compounds by
NaIO .ÐIn a 25 ml ¯ask equipped with magnetic stirrer, oxime
or phenylhydrazone (1 mmol) and CH Cl (10 ml) were added
to Mn(tpp)Cl (0.012 mmol) and tetrabutylammonium bromide
0.05 mmol). After addition of sodium periodate solution (2 mmol
in 10 ml H O) the mixture was stirred on a magnetic stirrer at
room temperature for 1 to 8 h. The progress of the reaction was
monitored by TLC (eluent: CCl /Et O). The organic phase was
puri®ed on a silica gel plate or silica gel column (eluent: CCl
Et O). Evaporation of the solvent a€orded the pure carbonyl
compound in 35±90% yields (Tables 1 and 2).
General Procedure for The Regeneration of Carbonyl Compounds
from Oximes by Bu NIO .ÐTo a solution of oxime (1 mmol) in
CH Cl (10 ml) were added Mn(tpp)Cl (0.012 mmol) and Bu NIO
2 mmol) and the solution stirred magnetically at room temperature
Received, 19th March 1998; Accepted, 27th April 1998
Paper E/8/02186D
4
2
2
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We are thankful to the Esfahan University Research
Council.