Specific features of the reaction of vanadyl acetylacetonate with tert-butyl hydroperoxide

Article abstract of DOI:10.1134/S1070363209080143

It was found for the first time that the reaction of N-(carboxyalkyl)ureas (ureido acids) with 4,5-dihydroxy-1,3-dimethyl-4,5-diphenylimidazolidin-2-one in methyl or isopropyl alcohol proceeds through the tandem sequence of α-ureidoalkylation and esterification to form the earlier unknown N-(carboxyalkyl)glycoluril methyl or isopropyl esters. N-(Carboxyalkyl)- glycolurils of a new-type substitution were obtained by alkaline hydrolysis of their isopropyl esters, the structure of one of them was confirmed by X-ray diffraction analysis.

Full text of DOI:10.1134/S1070363209080143

ISSN 1070-3632, Russian Journal of General Chemistry, 2009, Vol. 79, No. 8, pp. 1663–1670. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © L.P. Stepovik, M.V. Gulenova, 2009, published in Zhurnal Obshchei Khimii, 2009, Vol. 79, No. 8, pp. 1304–1310.
Specific Features of the Reaction of Vanadyl Acetylacetonate
with tert-Butyl Hydroperoxide
L. P. Stepovik and M. V. Gulenova
Lobachevskii Nizhnii Novgorod State University,
pr. Gagarina 23, Nizhnii Novgorod, 603950 Russia
e-mail: gulm@fambler.ru
Received January 12, 2009
Abstract—Reaction of vanadyl acetylacetonate with tert-butyl hydroperoxide (benzene, 20ºC) at any molar
ratio leads to the elimination of ligand and its oxidation mainly to CO2 and acetic acid. At the (acac)2VO:
t-BuOOH ratio above 1:10 liberation of oxygen partially in the singlet state takes place.
DOI: 10.1134/S1070363209080143
Vanadyl acetylacetonate I is a catalyst of oxidation
of various classes of organic compounds such as
secondary alcohols [1], amines [2], sulfides [3], of
epoxydation of alkenes [4, 5] and allyl alcohols [6],
etc. with hydrogen peroxide or tert-butyl hydro-
peroxide II. In many cases amount of hydroperoxide
essentially exceeds the amount of the substrate
oxidized, but no reasons of such situation are
presented. Different reaction schemes explaining the
formation of final products are offered.
The present work deals with the investigation of the
reaction of acetylacetonate I with hydroperoxide II at
various reagents ratio. The process was carried out in
benzene at 20ºC because no reaction with solvent was
observed at this temperature.
Due to the limited solubility of OV(acac)2 in
aromatic hydrocarbons its concentration was no more
than 0.01 mol l–1. When higher concentrations of
vanadyl were used addition of hydroperoxide caused
fast and complete dissolution of the precipitate. The
reaction is exothermic at any reagent ratio. The process
is accompanied by alteration in the coloration of
solutions from blue to dark green and light brown at
the vanadyl I:hydroperoxide II ratio varying from 1:2
to 1:4 and 1:15 respectively. In all the cases the
intermediate claret color was observed showing either
the formation of vanadyl(I) complexes with t-BuOOH
or the vanadium peroxocompounds [7, 10].
On the other side it is known that vanadyl acetyl-
acetonate catalyses the decomposition of secondary [7]
and tertiary [8, 9] hydroperoxides. Alkoxydioxo-
vanadate is suggested as a catalytically active particle
[7]. It is shown that about 20–30% of hydroperoxide
decomposes to form free radicals. In the products of
decomposition of cumyl hydroperoxide CO2 was found
[8]. Batyrshin et al. [9] have described decomposition
of hydroperoxide II according to the suggested
mechanism including the formation of the intermediate
complex OV(acac)2–2t-BuOOH. Activation of catalyst
and its regeneration proceed by means of reorganizing
the ligand surrounding of V+5. At the same time it was
marked that at the [t-BuOOH]: [catalyst] ratio above
7 black precipitate was formed what indicated the
decomposition of the latter. It was shown that 1 mole
of decomposed hydroperoxide I gave 0.33 mol of tert-
butanol by a nonradical process. No data on the
possible reaction of acetylacetonate ligands with
hydroperoxides and on the pathways of formation of
carbon dioxide was published.
The results obtained are listed in the table. The
presence of CO2, acetic and pyruvic acids, tert-
butylacetate, and tert-butylperacetate shows that the
destruction of acetylacetonate ligand takes place. In
spite of the significant difference in pKa between
acetylacetone and t-BuOOH, it can be probably
replaced by hydroperoxide [Eq. (1)].
(acac)2VO + t-BuOOH →← [(acac)2VO·t-BuOOH]
→
←
acacV(O)OOBu-t + MeCOCH2COMe,
(1)
A
Acetylacetone in the concentration equal to the
concentration of starting catalyst was found recently
1663

1664
STEPOVIK, GULENOVA
Bu-t
O
OH
C
H
C
H
O
VO(acac)2
CH3
CH3
C
O
CH2
C
O
CH3 + 2 t-BuOOH
C
CH3
O
OH
O
Bu-t
OH
C
(2)
CH3
CH3COCOCOCH3 + H2O.
C
O
C
CH3
_2t-BuOH
OH O
while treating vanadyl I with cyclohexyl peroxide at
10ºC [7]. No acetylacetone in free state was found by
us by means of GLC and the IR spectroscopy. It was
subjected to further oxidation to pentanetrione [11].
One of the possible pathways including the
nucleophilic addition of t-BuOOH to the carbonyl
group of diketone is presented in the scheme (2).
pentanetrione.
Subsequent reaction of pentanetrione with
hydroperoxode or the vanadium-containing peroxide
analogous to that of α-diketones must lead to the
mixed acetic-pyruvic anhydride. The latter may react
with t-BuOH or t-BuOOH to form the acetic and
pyruvic acids and also their tert-butyl esters and
peresters [11–13] found by us (see the table). But it
follows from the table that main reaction products of
conversion of acetylacetone are CO2 and acetic acid which
are found already at the equimolar reagents ratio. For
instance, at the 1:2 t-BuOOH:OV(acac)2 ratio the libera-
tion of CO2 was observed already on the third minute
of the propose. The participation of vanadium per-
oxides in oxidation may be seen from the alteration in
the color of the reaction solutions. In the experiment
described the claret coloration remained for 5 min. It
may be suggested that further oxidation of mixed
anhydride by the second α-dicarbonyl bond and hyd-
rolysis of the oxidation products would take place [Eq. (3)].
Peroxide A may also play the part of an oxidant of
acetylacetone. Then formation of vanadyl oxide acacV
(O)OV(O)acac must be expected together with
Products of the reaction of OV(acac)2 with t-BuOOH in
benzene at 20ºC (mol per mol of metal compound)
OV(acac)2:t-BuOOH
Reaction productsа
1:2
1:4
1:10
1:15
Volatile reaction products
O2
–
–
0.58
1.82
6.90
Traces
0.38
0.53
0.28
0.24
3.03
3.78
1.99
11.20
0.18
0.36
0.94
0.32
–
CO2
0.42
1.47
0.05
–
0.82
2.10
0.10
0.03
–
Equation (3) may serve as the confirmation of H2O
formation according to scheme (2). With the purpose
of testing the offered scheme the oxidation of
acetylacetone with hydroperoxide II in the presence of
vanadyl I was carried out at 10:20:1 molar ratio of
reagents in benzene at 20ºC. Conversion of β-diketone
was 40–50%. In this case 0.53 mol of CO2 and
0.90 mol of acetic acid per 1 mol of diketone were
isolated. The pentanetrione and its hydrate were also
synthesized and their reaction with t-BuOOH was
studied in benzene at 20ºC. The reaction of
pentanetrione with hydroperoxide II at 1:1 molar ratio
yielded 0.89 mol of t-BuOH, 0.59 mol of CH3COOH,
and 0.08 mol of tert-butyl acetate. The presence of CO2,
pyruvic acid, and unreacted triketone was established
t-BuOH
MeCO
(t-BuO)2
t-BuOOH
MeC(O)OBu-t
MeC(O)OOBu-t
СН3СООНb
–
0.15
0.05
0.81
0.12
0.12
1.22
3.21
Products of hydrolysis of the volatile residue
CH3COCH2COCH3
1.22
0.37
0.23
1.09
0.43
0.17
–
–
–
t-BuOH
RCOOHc
0.84
0.17
0.14
a
b
Mean results. Pyruvic acid was identified qualitatively as 2,4-
dinitrophenylhydrazone, and after treating with diazomethane its
methyl ester was found. c Mixture of acetic and pyruvic acids.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 8 2009

SPECIFIC FEATURES OF THE REACTION OF VANADYL ACETYLACETONATE
1665
t-BuOOH
CH3
CH3
CH3
C
O
C
O
C
O
CH3
C
O
O
C
O
C
O
_t-BuOH
t-BuOOH
_t-BuOH
(3)
CH3
+ H2O
CO2 + 2CH3COOH.
C
O
C
O
O
C
O
CH3
O
qualitatively. In the reaction of pentanetrione hydrate
with t-BuOOH at 1:2 molar ratio 0.60 mol of CO2 and
1.04 mol of CH3COOH were found [Eq. (3)].
concluded that the composition of vanadium-
containing precipitate is close to HOVO2·H2O.
Note that the IR spectrum of this precipitate is
identical to the ethylbenzene-insoluble product of
decomposition of the vanadium-containing peroxy-
derivative in the (t-BuO)4V–t-BuOOH system in the
presence of oxygen [14] [Eq. (4)].
In the IR spectra of volatile fractions of all the
reactions described intense absorption bands
characteristic of the acetic acid are observed, cm–1:
1714, 1760 [C=O (dimer, monomer), 1290 (C–O),
1420 (C–O–H). After treating with diazomethane the
acid was identified in a form of its methyl ester. At the
1:10 and higher molar ratio of vanadyl I and
hydroperoxide II alongside with the products of
transformation of the ligand the liberation of oxygen
was observed. In this case some part of VO(acac)2 is
converted to the dark-green precipitate insoluble in
benzene and containing no organic groups. Its IR
spectrum contains absorption bands at 600, 763 (V–O–V),
and 999 (V=O) cm–1. Very intense absorption band at
3409 cm–1 was attributed to the bond vibrations of
hydroxy group (V–OH), and the band at 1627 cm–1
was characteristic of the crystallization water (Fig. 1).
Elemental analysis data show that the residue contains
not more than 1% of carbon. Hydrogen content was
evaluated at 2.23, 2.57%, the calculated value for
HOVO2·H2O is 2.54%. Combustion of the substance
under study gives V2O3 and V2O5. On the basis of IR
spectroscopy and elemental analysis it may be
>V(O)OOCH(Me)Ph
(4)
>V(O)OH + PhC(O)Me.
In spite of the extremely poor solubility of the
precipitate in benzene it was found to decompose t-
BuOOH at room temperature with the liberation of
oxygen. Reaction of this precipitate with hydro-
peroxide II in benzene (0.45 g of t-BuOOH and 0.02 g
of precipitate, ~25:1 molar ratio) yielded 0.30 mol of
O2, 0.64 mol of t-BuOH, 0.05 mol of acetone and 0.04
mol of tert-butyl peroxide per 1 mol of hydroperoxide
II. Selectivity of oxygen formation was 60%.
Reaction of VO(acac)2 with t-BuOOH was studied
by means of ESR spectrocopy in the absence as well as
in the presence of spin traps such as 2-methyl-2-
nitrosopropane and C-phenyl-N-tert-butyl-nitrone at
20ºC. The first trap occured to be ineffective most
probably due to its oxidation to nitro compound. At the
cm–1
Т, %
3500 3000 2500 2000 1500 1000 500
100
95
90
85
80
75
3409.3
1627.52
70
65
60
Н
0.5 mT
998.932
Fig. 1. IR spectrum of the benzene-insoluble product
formed in the reaction of (acac)2VO with t-BuOOH excess
(1:15 molar ratio) (KBr pellet).
Fig. 2. ESR spectrum of (acac)2VO–t-BuOOH (1:15)
system registered just after mixing of reagents in the
absence of spin traps, benzene, 20ºC, c[(acac)2VO] 0.005 M.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 8 2009

1666
STEPOVIK, GULENOVA
addition of t-BuOOH to VO(acac)2 (2:1) in benzene
intensity of the vanadyl signal increased 3.5 times and
remained constant in the course of 30 min what
indicated the presence of the V4+ compounds. The
excess of hydroperoxide up to 10 mol/mol led to the
complete disappearance of the V4+ signal showing the
oxidation of V4+ to V5+. At the increase in the amount
of t-BuOOH to 15 mol per 1 mol of vanadyl I in the
absence of spin traps in benzene at 20ºC ESR spectrum
is a singlet, gi 2.0156 (Fig. 2).
registered in the(t-BuO)3VO–t-BuOOH system and
attributed to (t-BuO)2V(O)OO· radical [14].
On the basis of data on the reactions of aluminum
[15] and vanadium [14] tert-butylates with tert-
butylhydroperoxide we think that the formation of
oxygen in the reactions under study proceeds through
the stages of formation of vanadium-containing per-
oxides and trioxides.
Vanadium peroxy compounds may be formed due
to the displacement of ligand with hydroperoxide [Eq. (1)]
and also as the result of addition of t-BuOOH to V=O
bond [6, 7]. As it was shown above, excess hydro-
peroxide leads to substitution of ligands and formation
of the vanadium hydroxocompounds. The latter take
part in generation of oxygen, and the scheme of its
formation may be presented as follows [Eq. (5)].
Intensity of the signal does not alter in the course of
40 min. Analogous signal with gi 2.0150 is observed in
the course of decomposition of t-BuOOH on the
vanadium-containing precipitate. As t-BuOO. radicals
were not found under these conditions we suggested
that according to the value of g-factor the signal
belonged to the vanadium-containing >V(O)OO·
radical. A singlet with the same value of g-factor was
OH
OH
t-BuOOH
V
O + t-BuOOH
V
OOBu-t
V
O
O
O
Bu-t
O
H
t-Bu
O
O
H
O
V
1O2 + t-BuOH +
V
O.
O
Bu-t
(5)
_t-BuOH
B
Reaction of peroxide A with t-BuOOH according to
the analogous scheme also must lead to the liberation
of oxygen through the stage of the vanadium-
containing trioxide.
anthracene and 1,1-diphenylethylene [16] were carried
out [16]. It was established preliminary that Ph2C=CH2
does not react at room temperature with hydroperoxide
II (C6H6, 3 days).
Products of the reaction of anthracene with the
vanadyl I-t-BuOOH system at the 1:0.1:1.5 molar ratio
in benzene at 20ºC (1 day) contain 0.30 mol of
anthraquinone. Analogous reaction with 1,1-diphenyl-
ethylene yields 0.29 mol of benzoquinone and 0.20
mol of HCOOH. Formaldehyde was identified
qualitatively in the volatile reaction products, while the
products of hydrolysis contained epoxide, probably
1,1-diphenyloxirane.
Simultaneosly to formation of oxygen homolysis of
trioxide B takes place [scheme (6)] to give the
vanadium-containing peroxy radical traced by means
of ESR spectroscopy (Fig. 2).
a
V(OH)OO + t-BuO ,
(6a)
(6b)
B
b
V(OH)O + t-BuOO.
Indirect confirmation of the reaction (6b) is the
presence of tert-butylperoxide in the reaction products.
All the above-mentioned substances were formed in
the reaction of anthracene with tert-butylperoxide in
the presence of the insoluble precipitate isolated from
the reaction of VO(acac)2 with hydroperoxide.
Keeping of 0.02 g of the precipitate, 0.35 g of
anthracene, and 0.45 g of t-BuOOH in 20 ml of
benzene for 1 day yielded 0.08 g (20%) of anthra-
quinone, and after 3 days 0.17 g (41%) of it was found.
2t-BuOO· → t-BuOOBu-t + O2.
(7)
According to the scheme (5) oxygen must be
formed in the singlet state. With the purpose of
establishing this assumption reactions of the VO(acac)
2–t-BuOOH with the singlet oxygen acceptors such as
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SPECIFIC FEATURES OF THE REACTION OF VANADYL ACETYLACETONATE
1667
By an example of oxidation of 1,1-diphenylethylene it
was shown that the vanadium-containing precipitate
plays a role of heterogeneous catalyst. Small batch of
it, 0.01 g, was placed in 10 ml of benzene and kept for
1 h. After that the precipitate was filtered off and dried.
To the filtrate obtained 0.31 g of Ph2C=CH2 and 0.45 g
of t-BuOOH were added (1:3 molar ratio), and the
resulting mixture was kept at room temperature for
3 days. Only the traces of benzoquinone were found.
Then the solution obtained was treated with the batch
of precipitate isolated as described above. After 1 day
of storage at 20ºC 0.26 mol of Ph2CO and 0.18 mol of
formic acid were found. After 4 days amount of benzo-
quinone reached 0.36 mol, and after 7 days, 0.49 mol.
formaldehyde were evaluated as 2,4-dinitro-phenyl-
hydrazones by means of TLC 1 h after the beginning
of the reaction.
Formation of anthraquinone may be regarded as the
result of the reaction of anthracene either with the
singlet oxygen or with the vanadium-containing
trioxide through the stage of formation of 9,10
epidioxyanthracene [16]. Oxidation of Ph2C=CH2 to
benzoquinone and formaldehyde may occur with the
intermediate formation of 1,2-dioxetane and its
decomposition. It is known that the reactivity of 1,1-
diphenylethylene to the free singlet oxygen is low
[17], and we suggest that the reaction of phenylalkene
with the vanadium-containing trioxide takes place
[16].
Note that in the case of OV(acac)2 and the
vanadium-containing precipitate benzoquinone and
Ph2C
CH2 + [V]-OOOBu-t
Ph2C
O
CH2
O
Ph2CO + H2CO.
(8)
_[V]-OBu-t
Formaldehyde mainly forms formic acid or enters
the Condensation reactions.
was used. Volatile components (acetone, tert-butanol,
tert-butylperoxide, acetylacetone, methyl acetate) were
analysed on a 2400×3 mm column filled with TZKM
ceramic carrier containing 10% of PEGA, colunm
temperature 50–80ºC. Analysis of tert- butyl acetate
and tert-butyl peracetate was carried out on a 3000×3
mm column containing 5% of SP-2401 at 50ºC.
Analysis of high boiling products (acetophenone,
benzophenone, 1-phenyl-1-ethanol) was carried out on
a 3000×3 mm column, stationary phase 5% of SE-30
on Inerton-AW, column temperature 100–190ºC.
Anthracene, anthraquinone, and 1,1-diphenylethylene
were analysed at 190–210ºC on a 1000×3 mm column
filled with 5% of OV-17 on Inerton Super carrier.
Chromatograms were solved by means of the internal
standard method, in each case reference substances
were used. Amount of aliphatic acids in nonvolatile
residues was evaluated according to [18]. Carboxylic
acids were identified as methyl esters after treating
with diazomethane. Quantitative analysis of hydro-
peroxides was carried out by iodometric titration.
Carbonyl compounds were identified as 2,4-dinitro-
phenylhydrazones by melting points, and by means of
TLC comparing Rf values of the batch and reference
substances.
Hence, reaction of OV(acac)2 with the excess of t-
BuOOH proceeds through decomposition of vanadium
alkoxylate, oxidation of the ligand, and liberation of
oxygen partially in the singlet form through the stage
of formation of the vanadium-containing peroxides and
trioxides.
EXPERIMENTAL
IR spectra were recorded on an IR-Prestige-21
spectrometer from KBr pellets or thin layer. ESR
spectra were taken on a Bruker ER-200D-SRC
spectrometer equipped with a double ER 4105DR
resonator (working frequency 9.5 GHz), and the
temperature-controlling ER 4111VT block. For
evaluation of g factor diphenylpicrylhydrazyl was used
as a reference substance. Analysis was carried out in
the cell of ESR spectrometer. For the improvement of
resolution in the ESR spectra and removing of oxygen
liberating in the reaction of components I, II the reac-
tion solutions were degased. Spin traps were added on
the initial stages of the reactions. Vanadyl acetylaceto-
nate concentration was no more than 0.005 mol l–1.
Silpearl sorbent, the broad-pored silica gel on the
aluminum foil (Silufol UV-254) was used, elution was
carried out with benzene or 18:1 benzene–diethyl
ether. Amount of oxygen liberated in the course of the
reaction was measured by the amount of the benzoic
GLC analysis of the liquid reaction products was
carried out on a Tsvet-2-65 chromatograph equipped
with a flame ionization detector. Argon was used as a
carrier gas. In all the cases Chromaton N-AW- DMCS
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1668
STEPOVIK, GULENOVA
acid formed in the reaction of O2 with benzaldehyde
[19]. Vanadyl acetylacetonate was prepared from V2O5
by in treating succession with freshly distilled
acetylacetone and sodium carbonate solution [20], mp
252ºC [21].
observed. Its amount was evaluated by means of the
procedure [19]. For this purpose the reaction was
carried out in the H-shaped ampule. One of its bends
was loaded with 0.4 ml of benzaldehyde, and another
one with a solution of 0.088 g of VO(acac)2 and
0.449 g of tert-butyl hydroperoxide in 10 ml of
benzene. Both bends were frozen, degased, and sealed.
After refreezing vigorous liberation of oxygen was
observed, and the reaction solution aquired cherry
color. After 12 h formation of finely dispersed green
precipitate was observed, and the solution became light
brown. Amount of benzoic acid was evaluated by
weighting, and also by titration with 0.1 N NaOH
solution in presence of phenolophthaleine.
Pentanetrione-2,3,4 was prepared by oxidation of
acetylacetone with p-nitrosodimethylaniline, bp 55–
57ºC (12 mm Hg) [22]. Concentration of tert-butyl
hydroperoxide used was no less than 99.6–99.8%.
Reaction of vanadyl acetylacetonate with tert-
butyl hydroperoxide (1:15) in benzene, 20ºC. A
solution of 0.088 g of VO(acac)2 in 15 ml of benzene
was placed in a flask, and 0.448 g of t-BuOOH was
added. The reaction mixture immediately acquired
intense cherry coloration, and after 20 min it became
light brown. After 2 h formation of fine dark green
precipitate was observed. It was filtered off, and the
filtrate was analyzed chromatographically. tert-
Butanol, 0.27 g, tert-butyl peroxide, 0.017 g, 0.012 g
of tert-butyl acetate, and 0.0034 g of acetone were
found. By means of titration in the presence of FeCl3
[23] 0.005 g of tert-butyl peracetate was found.
Treating with diazomethane solution gave 0.075 g of
methyl acetate corresponding to 0.061 g of acetic acid.
Amount of benzoic acid was 0.30 g corresponding
to 0.040 g of O2 (3.78 mol per 1 mol of starting
vanadyl acetylacetonate). For the evaluation of CO2
liberated in the course of the reaction of VO(acac)2
with t-BuOOH the process was carried out in a two-
necked flask with the reflux condenser connected with
a bubbler filled with the saturated Ba(OH)2 solution.
Another neck was supplied with a tube for the inert gas
inlet. The flask was evacuated and then filled with dry
argon to remove oxygen. After that a mixture of 0.095 g
of VO(acac)2, 0.480 g of tert-butyl hydroperoxide, and
15 ml of benzene was placed in the flask, and the
argon flow was passed through it. Several minutes
later formation of barium carbonate was observed.
Argon was passed through the reaction mixture for 3 h
until the complete formation of the precipitate. BaCO3
was filtered off and dried. Yield 0.140 g, 1.99 mol/mol
of starting vanadyl.
The precipitate obtained as a greenish brown mass
was dissolved in diethyl ether, hydrolized with 10%
H2SO4, extracted with ether, and dried over Na2SO4.
Ether extract contained 0.02 g of t-BuOH. No tert-
butyl hydroperoxide was found in the reaction
products. In the parallel experiment the acid content
was evaluated in the precipitate obtained after filtering
the benzene solution [18]. Amount of carboxylic acids
was 0.17 mol per 1 mol of vanadyl. For their
identification the precipitate was treated with alkali,
the solution obtained was filtered, and water was
distilled off from the filtrate. The concentrated residue
was acidified with 30% sulfuric acid, thoroughly
extracted with the distilled diethyl ether, and dried
over Na2SO4. Some part of the solution was treated
with 2,4-dinitrophenylhydrazine to form the
corresponding hydrazone of the pyruvic acid which
was identified by means of TLC against the authentic
sample. Residual solution was methylated with
diazomethane and then treated with 2,4-dinitro-
phenylhydrazine to give the corresponding hydrazone
of methyl pyruvate, mp 184ºC in agreement with the
reported data [24].
Oxidation of acetylacetone with VO(acac)2–
t-BuOOH (10:1:20) system in benzene. A solution of
0.13 g of vanadyl I, 0.88 g of t-BuOOH, and 0.49 g of
acetylacetone was placed in the reaction vessel.
Twenty minutes later heat evolution was observed.
Amount of unreacted diketone after 20 h of keeping
was evaluated at 0.24 g. Volatile products were
recondensed in a trap cooled with liquid nitrogen.
Residual red-brown mass after a day of storage became
bluish green. Treating of the condensate with
diazomethane permitted to find 0.32 g of methyl
acetate. Amount of the acid (0.26 g) was confirmed
also by titration of the condensate with 0.1 N NaOH.
TLC analysis of volatile products before and after
treating the condensate with diazomethane permitted to
establish the formation of pyruvic acid and its methyl
ester (corresponding 2,4-dinitrophenylhydrazones were
found). In the parallel experiment formation of 0.51 g
In the reaction of VO(acac)2 with t-BuOOH at 1:15
molar ratio in benzene the liberation of oxygen was
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SPECIFIC FEATURES OF THE REACTION OF VANADYL ACETYLACETONATE
1669
of BaCO3 (0.53 mol per mol of diketone) was ob-
ACKNOWLEDGMENTS
served. In this case precipitation of the bluish green
solid from the solution was observed. Its IR spectrum
contained absorption bands characteristic of the acac-
V, V=O, and V–OH (3400 cm–1) bonds.
The work was carried out with the financial support
of Russian Fundation for Basic Research, grant no 08-
03-97050 p_povolzh’e-a.
Authors express their gratitude to the Doctor of
Chemical Sciences and the Correspondent Member of
Russian Academy of Sciences V.K. Cherkasov for the
help in recording and attributing the ESR spectra.
Reaction of anthracene with VO(acac)2-t-BuOOH
system (10:1:15) in benzene. VO(acac)2, 0.088 g,
0.5 g of anthracene, and 0.45 g of t-BuOOH in 40 ml
of benzene were in succession placed in the flask.
Reaction mixture aquired bright yellow color. After
24 h yellow needle-like crystals were filtered off on a
glass filter. Pure anthraquinone, 0.02 g, was obtained,
mp 280ºC (in agreement with the reported data). The
volatile products were recondensed, and 0.24 g of t-
BuOH and 0.06 g of (t-BuO)2 were found in this
preparation by chromatography. Yellow residue was
hydrolyzed in benzene with 10% sulfuric acid and
extracted with freshly distilled benzene. The extract
obtained was dried over sodium sulfate. Anthra-
quinone, 0.17 g, and 0.06 g of t-BuOH were found in
it. Aqueous acidic hydrolizate contained 0.02 g of t-
BuOH.
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