Aerobic oxidation of cumene catalysed by 4-Alkyloxycarbonyl-N- Hydroxyphthalimide

Article abstract of DOI:10.2478/s11532-014-0565-8

4-Hexyloxycarbonyl-, 4-dodecyloxycarbonyl- and 4-hexadecyloxycarbonyl-N- hydroxyphthalimides were synthesised using trimellitic anhydride chloride as the starting material. The obtained lipophilic derivatives of N-hydroxyphthalimide were applied as catalysts of the cumene oxidation reaction with oxygen performed in polar acetonitrile, in non-polar tert-butylbenzene and in the absence of a solvent. The courses of reactions catalysed by N-hydroxyphthalimide and its derivatives were compared. Versita Sp. z o.o.

Full text of DOI:10.2478/s11532-014-0565-8

Cent. Eur. J. Chem. • 12(11) • 2014 • 1176-1182
DOI: 10.2478/s11532-014-0565-8
Central European Journal of Chemistry
Aerobic oxidation of cumene catalysed
by 4-alkyloxycarbonyl-N-hydroxyphthalimide
Research Article
*
Kornela Kasperczyk, Beata Orlińska , Jan Zawadiak
Department of Chemical Organic Technology and Petrochemistry,
Silesian University of Technology, 44-100 Gliwice, Poland
Received 8 November 2013; Accepted 4 March 2014
Abstract: 4-Hexyloxycarbonyl-, 4-dodecyloxycarbonyl- and 4-hexadecyloxycarbonyl-N-hydroxyphthalimides were synthesised using trimellitic
anhydride chloride as the starting material. The obtained lipophilic derivatives of N-hydroxyphthalimide were applied as catalysts of the
cumene oxidation reaction with oxygen performed in polar acetonitrile, in non-polar tert-butylbenzene and in the absence of a solvent.
The courses of reactions catalysed by N-hydroxyphthalimide and its derivatives were compared.
Keywords: N-Hydroxyphthalimide derivatives • Cumene • Oxidation
©
Versita Sp. z o.o.
be oxidised in the presence of NHPI (10 mol%) and
an azo-initiator (3 mol%) to hydroperoxide with a high
1
. Introduction
The oxidation of cumene to hydroperoxide is an important yield of 77% when the process was performed at 75°C
industrial process [1]. Hydroperoxide is used for the for 6 h in acetonitrile (MeCN) as the solvent [8]. Several
synthesis of phenol (via the Hock method) and used as other isopropylaromatics were oxidised under the same
an oxidising agent of propylene in Sumitomo’s PO-only conditions, including 1,3- and 1,4-diisopropylbenzenes
process [2]. The Hock method can also be applied to the [8], 2,6- and 2,7-diisopropylnaphthalenes [9], and
synthesis of other valuable hydroxyaromatic compounds 1,3,5-triisopropylbenzene [10]. Recently, we reported
from isopropylarenes.
Recently, N-hydroxyphthalimide
the oxidation of other mono- and diisopropylaromatics
has (e.g. 4-isopropylbiphenyl, 1-isopropyl-4-
(NHPI)
been shown to be an effective catalyst in many methoxybenzene, 2-isopropylnaphthalene, 2-isopropyl-
oxidation processes [3,4], including the oxidation of 6-methoxynaphthalene, and 4,4’-diisopropylbiphenyl)
isopropylaromatics. In these processes, NHPI acts to hydroperoxides with a high yield (76-99%) using the
as a precursor of phthalimide-N-oxyl radical PINO, NHPI/AIBNcatalyticsystem, evenatamildertemperature
which effectively abstracts the hydrogen atom from of 60°C, using both oxygen and air under atmospheric
substrate. Many methods of PINO generation have been pressure and MeCN as the solvent [11]. The combination
reported including electrocatalytic, biocatalytic as well of NHPI and aldehyde has been reported by Melone et
as chemocatalytic systems [4,5]. The most often used al. [5,12]. Cumene hydroperoxide was obtained with
o
co-catalysts are transition-metal compounds. However, selectivity of 81% when cumene was oxidised at 25 C
when NHPI, in combination with transition metal for 6 h using NHPI (10 mol%) and CH CHO (10 mol%) in
3
compounds, has been used in the isopropylaromatics MeCN as a solvent (cumene conversion 36%).
oxidation processes, the selectivities to hydroperoxides
The use of NHPI as an organocatalyst in the
were low and products contained mainly respective isopropylaromatics oxidation processes has many
alcohols and ketones [6,7]. Therefore in order to obtain advantages, such as higher conversion and selectivity
hydroperoxides with high selectivity, metal-free systems to hydroperoxides and milder reaction conditions
are required. In 2001, Ishii reported that cumene could compared with non-catalysed and transition metal
*
E-mail: beata.orlinska@polsl.pl
1176

K. Kasperczyk, B. Orlińska, J. Zawadiak
catalysed processes. However, due to the low solubility 2. Experimental procedure
of NHPI in hydrocarbons, a polar solvent is necessary.
It can limit the possibility of NHPI implementation for Cumene (Merck) was purified by extraction with
industrial application [13]. Additionally, solvents such as concentrated sulphuric acid and distillation over sodium.
acetonitrile or acetic acid are hydrogen-bond acceptors Crystallisation of 2,2’-azobis(2-methylpropionitrile)
and form complexes with NHPI, resulting in decreased (AIBN) from ethanol was performed. Pyridine was
catalytic activity [14,15].
boiled with potassium hydroxide and distilled. The other
To the best of our knowledge, cumene has been starting materials were commercially available and
1
13
oxidised in the presence of NHPI and in the absence of used without further purification. The H and C NMR
solvent only by Koshel et al. [16]. The authors observed spectra were recorded in deuterated dimethyl sulfoxide
an increase in the reaction rate in the presence of (DMSO-d6) with a Varian Unity Inova-300 spectrometer.
NHPI under conditions similar to those used in industry HRMS data were recorded using a Waters Xevo G2 QTof
(
120°C). However, most likely due to the use of smaller Mass Spectrometer. Melting points were determined
amounts of NHPI and its unwanted decomposition at the in capillary tubes on an Electrothermal Melting Point
high temperature of 120°C, the obtained hydroperoxide Apparatus. A Waters Alliance 2690 HPLC equipped
yield was lower compared with those achieved in the with an autosampler, a UV detector (Waters photodiode
processes performed at lower temperature using array), and a Nova-Pak Silica 60 Å 4 µm column
10 mol% of NHPI and polar solvents [8-11].
(150×3.9 mm; Waters) was used with a mixture of
To eliminate the solvents Ishii et al. used in hexane and 2-propanol as the mobile phase (99:1 v/v)
-1
the oxidation process of cyclohexane, lipophilic at a flow rate of 1.0 mL min .
derivatives of NHPI, such as 4-alkyloxycarbonyl-N-
hydroxyphthalimides [17] and its fluorinated derivatives 2.1. Typical procedure for cumene oxidation
[
18], were used as catalysts. The processes were The cumene oxidations were performed in a gasometric
performed at 100°C under an air pressure of 1 MPa for
4 h in the presence of Co(II) and Mn(II) salts
apparatus as shown in Fig. 1.
1
The cumene, the catalyst, AIBN and, in some cases,
and 0.08 mol% of the NHPI derivatives. Among the solvent (tert-butylbenzene or acetonitrile) were
4-hexyloxycarbonyl-,
4-dodecyloxycarbonyl-
and placed in a 10 mL flask connected to a gas burette filled
4-tetradecyloxycarbonyl-N-hydroxyphthalimides, the last with oxygen under atmospheric pressure. The oxygen
two showed the highest activity. The NHPI derivatives uptake was measured and used to calculate the cumene
containing long, fluorinated alkyl chains as substituents conversion (after recalculation to standard conditions of
were also active, but their synthesis was more complex. 273 K and 1 atm).
The influence of the introduction of a substituent
to the NHPI aromatic ring on the catalytic activity has
been described previously. Wentzel et al. [19] and
Annunziatini et al. [20] observed an increase in the α – conversion, nO2 – mmols of oxygen consumed at
rate of the oxidation reaction of ethylbenzene and normal conditions, n – mmols of hydrocarbon
benzyl alcohol by increasing the electron-withdrawing
The amount of cumene hydroperoxide was
properties of the substituent. In contrast, Novikova determined iodometrically according to the described
et al. [21] and Kushch [22] observed that the rate of method [23], and the result was used for calculation of
cumene oxidation decreased due to the introduction of selectivity.
an electron-withdrawing carboxyl group (4-COO-). The
n−OOH
influence of the electron-withdrawing substituent on the
increase in the BDE value of NO-H and the stabilisation
of the transition state of the hydrogen abstraction
S−OOH
=
⋅100%
nO2
reaction by the N-oxyl radical was discussed in previous S-OOH – hydroperoxide selectivity, n-OOH – mmols of
publications [19-22].
In this study,
hydroperoxide groups based on iodometric analysis, nO2
4-alkyloxycarbonyl-N- – mmols of oxygen consumed at normal conditions.
the
hydroxyphthalimides were synthesised and used
The amounts of 2-phenyl-2-propanol and
as catalysts of the cumene oxidation processes to acetophenone were determined by HPLC according to
hydroperoxide performed in polar and non-polar media the method described in [24].
under mild reaction conditions.
1177

Aerobic oxidation of cumene catalysed by
-alkyloxycarbonyl-N-hydroxyphthalimide
4
Figure 1. Gasometric apparatus: (1) magnetic stirrer (2) flask (3) rubber stopper (4) Liebig condenser (5) levelling bulb (6) gas burette (7) valve.
2
.2. Synthesis of 4-alkyloxylcarbonyl-N-
(
Ar), 66.3 (COO-CH -), 31.6 (OCH -CH -), 28.7 (˗CH -),
2 2 2 2
hydroxyphthalimide using trimellitic 25.8 (-CH -), 22.7 (-CH CH ), 14.6 (-CH ); HRMS (ESI)
anhydride chloride
2
2
3
3
-
calc. for C H NO [M-H] 290.1029, found 290.1021;
15 16 5
Pyridine (20 mmol, 1.5 mL) was added in a few portions mp 80÷82°C (benzene); 19% yield.
to a stirred mixture of trimellitic anhydride chloride (20
1
2: H NMR (300 MHz DMSO-d6): δ 11.01 (s, 1H,
mmol, 4.2 g) in toluene (10 mL) at 0ºC. Next, a solution N-OH), 8.33 (dd, J = 7.8, 1.5 Hz, 1H, Ar-H), 8.16 (s, 1H,
of hexyl, dodecyl or hexadecyl alcohol (20 mmol) in Ar-H), 7.95 (d, J = 7.8 Hz, 1H, Ar-H), 4.31 (t, J = 6.5 Hz,
toluene (10 mL) was added dropwise over 30 min. 2H, CO-OCH -), 1.67 - 1.74 (m, 2H, OCH -CH -), 1.21
2
2
2
The mixture was stirred for 4 h at room temperature, - 1.38 (m, 18H, -CH -), 0.83 (t, J = 6.9 Hz, 3H, -CH ),
2
3
13
then for 10 h at 85ºC and for 7 h at 100ºC. Toluene
C NMR (75 MHz DMSO-d6): δ 164.9 (Ar-CO-N), 163.9
was evaporated, and product in form of white paste was (Ar-CO-N), 135.9 (Ar), 135.7 (Ar), 133.2 (Ar), 130.1 (Ar),
obtained. Dried pyridine (25 mL) and hydroxylamine 124.2 (Ar), 123.3 (Ar), 66.3 (COO-CH2-), 32.0 (OCH2-
hydrochloride (22 mmol, 1.52 g) were added and CH2-), 29.7 (-CH2-) 29.6 (-CH2-), 29.5 (-CH2-), 29.4
the reaction mixture was stirred at 90ºC for 15 h. (-CH2-), 28.7 (˗CH2-), 26.1 (-CH2-), 22.8 (-CH2CH3),
-
A portion of the pyridine (approximately 15 mL) was 14.6 (-CH3); HRMS (ESI) calc. for C H NO [M-H]
21
28
5
evaporated, and the product was poured to 10 mL 374.1968, found 374.1973; mp 102÷104.5°C (MeOH);
of water and acidified by hydrochloric acid (11 M) to 67% yield.
1
pH 1. The precipitate was filtered, and poured into water,
3: H NMR (300 MHz DMSO-d6): δ 11.02 (s, 1H,
and acidified again. The product was recrystallised N-OH), 8.35 (d, J = 7.7 Hz, 1H, Ar-H), 8.16 (s, 1H, Ar-H),
twice from benzene (compound 1) or methanol 7.96 (d, J = 7.8 Hz, 1H, Ar-H), 4.31 (t, J = 6.3 Hz, 2H,
(
compounds 2 and 3).
CO-OCH -), 1.68 - 1.77 (m, 2H, OCH -CH -), 1.20 - 1.38
2
2
2
1
13
1
: H NMR (300 MHz DMSO-d6): δ 11.00 (s, 1H, (m, 26H, -CH -), 0.83 (t, J = 6.6 Hz, 3H, -CH ), C NMR
2
3
N-OH), 8.33 (dd, J = 7.8, 1.4 Hz, 1H, Ar-H), 8.15 (s, (75 MHz DMSO-d6): δ 164.9 (Ar-CO-N), 163.9 (Ar-
H, Ar-H), 7.95 (dd, J = 7.8, 0.6 Hz, 1H, Ar-H), 4.31 (t, CO-N), 135.9 (Ar), 133.2 (Ar), 130.1 (Ar), 124.2 (Ar),
J = 6.5 Hz, 2H, CO-OCH -), 1.67 - 1.76 (m, 2H, OCH - 123.3 (Ar), 66.3 (COO-CH -), 32.0 (OCH -CH -), 29.7
1
2
2
2
2
2
CH -), 1.27 - 1.39 (m, 6H, -CH -), 0.85 (t, J = 3.5 Hz, (-CH -) 29.4 (-CH -), 29.3 (-CH -), 28.7 (˗CH -), 26.1
2
2
2
2
2
2
1
3
3
H, -CH ), C NMR (75 MHz DMSO-d6): δ 175.6 (Ar- (-CH -), 22.8 (-CH CH ), 14.6 (-CH ); HRMS (ESI) calc.
3
2 2 3 3
-
COOCH ), 165.0 (Ar-CO-N), 163.9 (Ar-CO-N), 135.9 for C H NO [M-H] 430.2595, found 430.2619; mp
2
25 36
5
(
Ar), 135.7 (Ar), 133.2 (Ar), 130.1 (Ar), 124.2 (Ar), 123.3 110.7÷111.2°C (MeOH); 16% yield.
1178

K. Kasperczyk, B. Orlińska, J. Zawadiak
Scheme 1. Preparation of 4-alkyloxycarbonyl-N-hydroxyphthalimides. Reagents and conditions: (I) alcohol, toluene, 4 h - rt, 10 h - 85ºC,
7
h - 100ºC; (II) hydroxylamine hydrochloride, pyridine, 90ºC, 15 h.
Scheme 2. Preparation of 4-dodecyloxycarbonyl-N-hydroxyphthalimide. Reagents and conditions: (I) hydroxylamine hydrochloride, pyridine,
0ºC, 15 h; (II) dodecyl alcohol, p-toluenesulphonic acid, hexane, 6-10 h, 70ºC.
9
2
.3. Synthesis of N-hydroxyphthalimide-4-
carboxylic acid from trimellitic anhydride
4
-carboxylic acid, as revealed by TLC analysis (using
aluminium plates coated with silica gel 60 F254 (Merck)
Trimellitic anhydride (200 mmol, 38.4 g) and and a methanol/chloroform 3:2 v/v solvent system).
hydroxylamine hydrochloride (220 mmol, 13.9 g) were The H NMR spectra determined a negligible amount of
1
added to 250 mL of pyridine and stirred at 90ºC for 15 h. 4-dodecyloxycarbonyl-N-hydroxyphthalimide.
The product was poured into water (400 mL), acidified
with 11 M hydrochloric acid (55 mL) and maintained at
3
. Results and discussion
5ºC for 16 h. The precipitate was filtered, poured into to
0 mL of water and acidified by 11 M hydrochloric acid
2
(
2.5 mL) again. The product was dried under vacuum.
3.1. Synthesis of the lipophilic derivatives of NHPI
1
H NMR (300 MHz DMSO-d6): δ 10.98 (s, 1H, N-OH), The 4-hexyloxycarbonyl- (1), 4-dodecyloxycarbonyl- (2)
.32 (ddd, J = 7.7, 2.4, 1.5 Hz, 1H, Ar-H), 8.14 (dd, and 4-hexadecyloxycarbonyl-N-hydroxyphthalimides
J = 1.4, 0.7 Hz, 1H, Ar-H), 7.92 (dd, J = 7.7, 0.7 Hz, (3) were synthesised by a two-step method using
8
13
1
H, Ar-H), C NMR (75 MHz DMSO-d6): δ 166.4 (Ar- trimellitic anhydride chloride as the starting material
CO-N), 164.0 (Ar-CO-N), 136.9 (Ar), 136.0 (Ar), 132.9 (Scheme 1). Compound 3 has not been synthesised
Ar), 129.92 (Ar), 124.0 (Ar),123.5 (Ar); mp 230-231°C; before. The properties of compounds 1 and 2 that were
3.1% yield.
not given in a previous paper [17] were determined.
(
3
We
attempted
also
to
synthesise
2
.4. Synthesis of 4-dodecyloxylcarbonyl-
N-hydroxyphthalimide
N-hydroxyphthalimide-4-carboxylic acid
4
-dodecyloxycarbonyl-N-hydroxyphthalimide
using
using trimellitic anhydride as the starting material, in
accordance with a previous study [17] (Scheme 2).
N-hydroxyphthalimide-4-carboxylic acid (10 mmol, However, this method was found to be less effective.
.1 g), dodecyl alcohol (20 mmol, 3.72 g) and A reaction of anhydride with hydroxylamine produced
2
p-toluenesulphonic acid (1 mmol, 0.2 g) were added 4-carboxyl-N-hydroxyphthalimide; however, in the
to 40 mL of hexane. The reaction mixture was subsequent step consisting of a reaction with alcohol, a
refluxed for 10 h, and the precipitate was filtered. The mixture of unreacted acid and a small amount of ester
product contained unreacted N-hydroxyphthalimide- was obtained.
1179

Aerobic oxidation of cumene catalysed by
4-alkyloxycarbonyl-N-hydroxyphthalimide
Table 1. Oxidation of cumene with NHPI derivatives in polar and non-polar solvents.
a
N°
Catalyst
Conversion [%]
Selectivity [%]
Solvent
1
2
3
4
5
6
7
8
9
1
.
Non
NHPI
1
5
100
100
100
100
100
100
100
100
100
100
MeCN
MeCN
MeCN
MeCN
MeCN
t-BuPh
t-BuPh
t-BuPh
t-BuPh
t-BuPh
.
50
49
40
40
2
.
.
2
.
3
.
Non
NHPI
1
.
11
30
32
35
.
.
2
0.
3
6
0ºC; 1 atm.; 1000 rpm; 6 h. Cumene (0.7 mL, 5 mmol); catalyst (5 mol%); AIBN (0.025 g); solvent (5 mL).
a
Calculated based on oxygen consumption and iodometric analysis.
Catalysts 1-3 were soluble in the reaction mixture
within 10-15 min of the reaction time when both MeCN
and tert-butylbenzene were used. In contrast, a large
portion of NHPI remained insoluble in the reaction using
tert-butylbenzene, and, therefore, a lower conversion
of cumene was obtained (entry 7). The comparison
of the processes catalysed by 1-3 performed in tert-
butylbenzene and MeCN showed that the oxidation
reaction rates were lower in the non-polar conditions.
To obtain a higher conversion of cumene in a non-
polar solvent (48%), the process using catalyst 3 was
performed for 13 h (Fig. 2).
The cumene conversion slightly decreased with the
length of the alkyl group in the processes performed
in MeCN and increased in those performed in tert-
butylbenzene. This result suggests that the observed
effects resulted from the small differences in the catalyst
solubility in the mixture.
Figure 2. Oxidation of cumene with NHPI derivatives in a non-polar
solvent. ( ) 5.0 mol% C16-NHPI; ( ) 5.0 mol% C12- 3.3. Catalytic cumene oxidation in the absence
NHPI; ( ) 5.0 mol% C6-NHPI; ( ) 5.0 mol% NHPI; (
.0 mol% NHPI
)
of a solvent
0
The cumene oxidation processes in the presence of
compounds 1-3 were also performed in the absence of
3
.2. Catalytic cumene oxidation in polar and a solvent. The influence of the catalyst amount on the
non-polar solvents
course of the oxidation reaction was studied using the
The lipophilic NHPI derivatives 1-3 in an amount of most lipophilic derivative, catalyst 3.
mol% were used as catalysts in the cumene oxidation
The results presented in Fig. 3 demonstrated that
5
processes performed both in polar acetonitrile and in the highest reaction rate was obtained when 1 mol% of
non-polar tert-butylbenzene as solvents under mild compound 3 was used. When higher amounts of catalyst
reaction conditions (60ºC, 0.1 MPa). It has been were applied, a portion of the catalyst remained insoluble
reported previously [11] that hydroperoxide and in the mixture and negatively influenced the process.
NHPI were stable at these conditions. The processes
were compared with those catalysed by NHPI compounds 1-3 and NHPI as catalysts were compared
Table 1).
(Table 2, Fig. 4).
Therefore, the processes using
1
mol% of
(
1180

K. Kasperczyk, B. Orlińska, J. Zawadiak
Figure 3. Oxidation of cumene with different amounts of C16-NHPI
Figure 4. Oxidation of cumene with NHPI derivatives in the absence
in the absence of solvent. ( ) 0.1 mol%; ( ) 0.5 mol%;
of a solvent. ( ) 1.0 mol% C16-NHPI; ( ) 1.0 mol% C12-
(
) 1.0 mol%; ( ) 2.0 mol%; ( ) 2.5 mol%.
NHPI; ( ) 1.0 mol% C6-NHPI; ( ) 1.0 mol% NHPI; (
.0 mol% NHPI.
)
0
Table 2. Oxidation of cumene with NHPI derivatives in the absence
were initially significantly higher than those using NHPI
because of their higher solubility in the studied system.
However, the rates changed after approximately 2 h of
reaction. The observed decrease in the reaction rates
in the processes using compounds 1-3 could be a result
of inhibitor formation and/or catalyst decomposition.
However, further studies are needed to explain this
phenomenon. It is known that N-oxyl radicals can be
unstable at higher temperature and decompose to
inactive compounds. For example, Ishii et al. have
reported that a portion of the lipophilic derivatives of
of a solvent.
N°
Catalyst
Conversion
%]
Selectivitya
[%]
[
1.
2.
3.
4.
5.
Non
NHPI
1
11
22
22
23
26
100
100
100
2
100b
100c
3
6
0ºC; 1 atm.; 1000 rpm; 6 h. Cumene (2.0 mL, 14.3 mmol); catalyst NHPI was changed to the corresponding phthalimide
(
1 mol%); AIBN (0.025 g).
in the studied cyclohexane oxidation at 100°C under a
pressure of 1 MPa. On the other hand, we demonstrated
previously [11] that NHPI was stable under mild
conditions (60°C, 0.1 MPa), which were applied in
present studies. The cumene oxidation is typically
autoinhibited by the phenol that is formed in the acid
catalysed rearrangement reaction of hydroperoxide
a
Calculated based on oxygen consumption and iodometric analysis.
The HPLC analysis demonstrated that the selectivity to hydroperoxide
was slightly lower. The presence of 2-phenyl-2-propanol in the mixture was
observed (acetophenone was not detected); the selectivity to 2-phenyl-2-
propanol calculated based on HPLC was 2.1%.
b
c
The HPLC analysis demonstrated that the selectivity to hydroperoxide
was slightly lower. The presence of 2-phenyl-2-propanol in the mixture was
observed (acetophenone was not detected); the selectivity to 2-phenyl-2-
propanol calculated based on HPLC was 1.8%.
[
25]. The high selectivity to hydroperoxide that was
Similar to the processes performed in non-polar found in this study implied that autoinhibition did not
tert-butylbenzene, the highest conversion was obtained occur. However, even traces of phenol can retard the
using the most lipophilic derivative, compound 3, as free radical processes.
the catalyst. The slight increase in the conversion with
Valuable results were also obtained using NHPI as
increasing alkyl chain length was also observed. This the catalyst in the absence of a solvent. At the beginning
result is in accordance with the results reported by Ishii of the reaction, a portion of the NHPI remained insoluble
et al. for cyclohexane oxidation [17].
in the mixture, but its solubility steadily increased
The courses of the reactions catalysed by with the progress of the reaction (the mixture became
compounds 1-3 and NHPI differed significantly. The transparent after approximately 110 minutes). The
rates of the oxidation reactions using compounds 1-3 increase in solubility was a result of the hydroperoxide
1181

Aerobic oxidation of cumene catalysed by
-alkyloxycarbonyl-N-hydroxyphthalimide
4
formation that caused an increase in the polarity of rates of cumene oxidation reactions performed in tert-
the reaction mixture. This result was confirmed by the butylbenzene were higher in the presence of catalysts
comparison of the solubility of NHPI in cumene and 1-3 than NHPI because their higher solubility in non-
its solubility in a solution of cumene hydroperoxide polar media (e.g. the cumene conversion of 11 and 35%
(
10 weight %) and cumene. At 60°C, the NHPI solubility were achieve using NHPI and compound 3 as catalyst,
was 0.03 and 0.055 g cm in cumene and in the respectively; 60°C, 6 h).
hydroperoxide solution, respectively.
Valuable results were obtained in the processes
-3
performed in the absence of a solvent. As expected,
the rates of oxidation reactions using compounds 1-3
were initially significantly higher than those using NHPI
because of their higher solubility in the studied system.
4
. Conclusions
The derivatives of NHPI, 4-hexyloxycarbonyl-, However, the solubility of NHPI in the system steadily
-dodecyloxycarbonyl- and 4-hexadecyloxycarbonyl-N- increased as a result of polarity increase caused by
4
hydroxyphthalimides, were synthesised using trimellitic hydroperoxide formation. Therefore, the conversions
anhydride chloride as starting material. The synthesis obtained after 6 h of oxidation reaction catalysed by
was more effective compared with the described NHPI and lipophilic derivatives were similar.
previously method using trimellitic anhydride as a
substrate [17].
The lipophilic derivatives 1-3 showed catalytic activity Acknowledgements
in the cumene oxidation processes performed in polar
(MeCN) and non-polar (tert-butylbenzene) solvents Financial assistance from the National Science Centre
as well as in the absence of solvents. Their catalytic of Poland (Grant No. N N209 755440) is gratefully
activity in MeCN was comparable to NHPI. However, the acknowledged.
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C. Punta, J. Chem. Technol. Biotechnol., DOI:
0.1002/jctb.4213
Antioxidants in Organic Chemistry and Biology
(CRC Press, Boca Raton 2005) pp. 495-540
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