Binuclear iron(III) phthalocyanine(μ-oxodimer)-catalyzed oxygenation of aromatic hydrocarbons with iodosylbenzene sulfate and iodosylbenzene as the oxidants

Article abstract of DOI:10.1002/adsc.200900705

Two binuclear iron(III) phthalocyanine-(μ-oxodimer) complexes were tested in catalytic oxygenation reactions of several aromatic hydrocarbons using iodosylbenzene (PhIO)_n or oligomeric iodosylbenzene sulfate [(PhIO)₃SO₃]_n as the oxidants. Results of this study demonstrate that [(PhIO)₃SO₃]_n is the most reactive oxygenating reagent that can be used as a safe and convenient alternative to the thermally unstable and potentially explosive iodosylbenzene. The pyridine-containing binuclear μ-oxobis-{iron(III)-pyridino[3,4]-9(10), 16(17),23(24)-tri-tertbutyltribenzoporphyrazine} is significantly more active as compared to the traditional μ-oxobis[iron-(III)-2,9(10),16(17),23(24)-tetra- tert-butylphthalocyanine].

Full text of DOI:10.1002/adsc.200900705

FULL PAPERS
DOI: 10.1002/adsc.200900705
Binuclear Iron(III) Phthalocyanine(m-Oxodimer)-Catalyzed
G
Oxygenation of Aromatic Hydrocarbons with Iodosylbenzene
Sulfate and Iodosylbenzene as the Oxidants
Heather M. Neu,a Mekhman S. Yusubov,a,b Viktor V. Zhdankin,a,*
and Victor N. Nemykina,*
a
Department of Chemistry and Biochemistry, University of Minnesota Duluth, Duluth, MN 55812, USA
Fax : (+1)-218-726-7394; phone: (+1)-218-726-6729; e-mail: vzhdanki@d.umn.edu or vnemykin@d.umn.edu
Siberian State Medical University and Tomsk Polytechnic University, 2 Moskovsky trakt, 634050 Tomsk, Russia
b
Received: October 10, 2009; Published online: December 10, 2009
Abstract: Two binuclear iron
oxodimer) complexes were tested in catalytic oxy- butyltribenzoporphyrazine} is significantly more
genation reactions of several aromatic hydrocarbons active as compared to the traditional m-oxobis[iron-
using iodosylbenzene (PhIO)n or oligomeric iodosyl- (III)-2,9(10),16(17),23(24)-tetra-tert-butylphthalocya-
A
ACHTUNGTRENU{NGN ironACHNUTRTGEG(NNUN III)-pyridinoCAHTNUGTREN[GUNN 3,4]-9(10),16(17),23(24)-tri-tert-
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
benzene sulfate [(PhIO)3SO3]n as the oxidants. Re- nine].
sults of this study demonstrate that [(PhIO)3SO3]n is
the most reactive oxygenating reagent that can be
used as a safe and convenient alternative to the ther- Keywords: iodine; iodosylbenzene; iodosylbenzene
mally unstable and potentially explosive iodosylben- sulfate; iron phthalocyanine m-oxodimer; oxygena-
zene. The pyridine-containing binuclear m-oxobis- tion
Introduction
The catalytical properties of transition metal porphyr-
ins, phthalocyanines, and related compounds have
been well-documented within the last 50 years.[1] As it
Figure 1. Hypervalent iodine oxidants: iodosylbenzene 1 and
oligomeric iodosylbenzene sulfate 2.
was shown recently, porphyrin and phthalocyanine
iron (III) m-oxo-,[2a–c] and m-nitrido-dimers,[2d,e] which
were earlier considered as catalytically inactive com-
pounds, in many cases have high catalytic activity in
different oxidation reactions. Traditionally, hydrogen low thermal stability and explosive properties upon
peroxide and organic peroxides were used as the oxi- moderate heating.[7] We have recently shown that the
dants for transition metal porphyrin-type-catalyzed m-oxobis
ACHUTGTNRNEUG[N ironACHTUNGTNER(NUGN III)-2,9(10),16(17),23(24)-tetra-tert-but-
reactions.[3] These oxidants, however, can be involved
AHCTUNGTRENNUNG
into parallel one- and two-electron transfer reactions, oxidation of a variety of organic substrates with hy-
which often compromise the selectivity of catalytic re- pervalent iodine reagents.[8] In particular, the oligo-
actions.
meric iodosylbenzene sulfate [(PhIO)3SO3]n (2) was
Hypervalent iodine compounds are versatile, selec- proven to be an excellent alternative to iodosylben-
tive oxidants that have the added advantage of being zene in transition metal phthalocyanine- and porphy-
biodegradable and low in toxicity.[4,5] Among these re- rin-catalyzed reactions.
agents, iodosylbenzene, (PhIO)n (1) (Figure 1), is,
probably, the mostly used oxygen transfer agent,[5] parative reactivity of the well-known compound 3 and
which has also found widespread application in vari- new iron(III) phthalocyanine m-oxodimer 4 (Figure 2)
In this paper, we report preliminary results on com-
AHCTUNGTRENNUNG
ous transition metal porphyrin catalyzed oxygenation in the biomimetic oxidation of several aromatic com-
reactions.[6] Despite its usefulness as an oxidant, prac- pounds using traditional iodosylbenzene (1) and the
tical applications of iodosylbenzene are hampered by new hypervalent iodine reagent 2 (Figure 1) as termi-
its low solubility in non-reactive media,[5] as well as its nal oxidants.
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Binuclear IronACHTUNGTRENNUNG(III) Phthalocyanine(m-Oxodimer)-Catalyzed Oxygenation
FULL PAPERS
Figure 2. IronACHTUNGTRENNUNG(III) phthalocyanine-(m-oxodimer) 3 and 4.
Results and Discussion
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
The oligomeric iodosylbenzene sulfate [(PhIO)3·SO3]n There are two main reasons for testing the catalyst 4.
2 was prepared by simple treatment of commercially First, the introduction of a fused pyridine ring into
available (diacetoxyiodo)benzene with aqueous the phthalocyanine core increases its first oxidation
sodium hydrogen sulfate and isolated as a thermally potential. Second, the nitrogen atom of the pyridine
stable, yellow crystalline solid.[8] Complex 3 was pre- ring can serve as an effective axial group, which can
pared using a direct high-temperature reaction be- be coordinated to one iron
tween 4-tert-butylphthalonitrile and iron(II) acetate as the electron density on the second iron
described previously,[9] while preparation of the new
The results of the catalytic oxidation of anthracene
catalyst 4 is based on the metallation reaction of 5, 2-tert-butylanthracene 8, 2-methylnaphthalene 12,
asymmetric metal-free m-oxobis[iron(III)-pyridino- 9,10-phenanthrene 16, and adamantane 20 using hy-
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
A
ACHTUNGTRENNUNG
Table 1. Catalytic oxidations of aromatic hydrocarbons and adamantane using oxidants 1 and 2 and catalysts 3 and 4.
Entry
Catalyst
(mol%)
Oxidant
(mol equiv)
Solvent
T
Time
[h]
Conversion (isolated
yield) [%]
Product distribution
[%]
G
[oC]
1
2
3
4
5
6
7
8
none
none
2 (4.5)
2 (4.5)
2 (4.5)
2 (4.5)
2 (6)
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
toluene
toluene
MeOH
MeOH
MeOH
25
25
25
25
25
25
25
25
25
25
0
1
24
1
24
1
5
1.1
74
0.5
25
0.4
2.8
100
100
100
100
100
6 (100)
6 (48)
6 (100)
6 (59)
7 (52)
Py (225)
Py (225)
Fe3+ (100)[a]
Fe3+ (100)[a]
3 (10)
3 (10)
4 (10)
7 (41)
7 (100)
7 (100)
2 (6)
1 (7.5)
2 (7.5)
1 (12)
2 (6)
5
6 (100)
6 (100)
6 (100)
6 (85)
2[8b]
2
9
10
11
4 (15)
4 (15)
2
2.5
7 (15)
7 (10)
2 (6)
6 (90)
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Heather M. Neu et al.
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Table 1. (Continued)
Entry
Catalyst
(mol%)
Oxidant
(mol equiv)
Solvent
T
Time
[h]
Conversion (isolated
yield) [%]
Product distribution
[%]
G
[oC]
12
13
3 (15)
4 (15)
2 (6)
2 (4.5)
toluene
MeOH
25
25
20[8b]
0.5
100 (72)
100
9 (100)
9 (76)
10 (13)
11 (11)
14
15
16
17
3 (30)
4 (15)
4 (30)
4 (5)
2 (6)
2 (6)
2 (4.5)
2 (6)
toluene
MeOH
MeOH
MeOH
25
25
0
24
2
3
1.3
89
87
96
13 (55)
13 (32)
13 (39)
13 (33)
14 (45)
14 (26)
14 (30)
14 (10)
15 (42)
15 (31)
15 (57)
25
3
18
19
20
21
22
23
3 (15)
3 (30)
4 (15)
4 (45)
4 (30)
4 (5)
2 (6)
2 (6)
2 (6)
2 (6)
2 (6)
2 (6)
toluene
toluene
MeOH
MeOH
MeOH
MeOH
25
25
25
25
0
2.5
4
2.5
3.5
4
0
2
17 (100)
17 (13)
82 (50.5)
93
44
18 (66)
18 (59)
18 (33)
18 (84)
19 (21)
19 (41)
19 (27)
19 (5)
17 (40)
17 (11)
25
3
100
24
25
26
27
3 (15)
3 (45)
4 (15)
4 (30)
2 (6)
2 (6)
2 (6)
2 (6)
toluene
toluene
MeOH
MeOH
25
25
25
0
24
24
24
24
0
1.8
2.4
0
21 (100)
21 (100)
[a]
FeACHTUNGTRENNUNG(III) acetate was used as a source of the FeACHTUGNTREN(NUNG III) ions.
pervalent oxidants 1 and 2 and catalysts 3 and 4 are formed under these reaction conditions. Methanol
presented in Table 1. The use of iodosylbenzene and was found to be the best solvent for the oxidations in
oxidant 2 in the first reaction in the presence of m- the presence of m-oxodimer 4, while toluene was used
oxo
ture.[8b]
All oxidation reactions were carried out in dry
ACHTUNGTRENNUNGdimer 3 was previously reported in the litera- for the reactions catalyzed by m-oxodimer 3 as previ-
G
ously discussed.[8]
As we have shown earlier,[8b] the oxidation of an-
methanol or in toluene using 1.5–2.5 times excess thracene with hypervalent iodine reagents 1 and 2 in
(4.5–7.5 mol equiv of active oxygen per 1 molecule of the absence of catalysts at room temperature in tolu-
substrate) with 0.10–0.45 equiv. of the catalyst 3 or 4 ene or at 408C in dichloromethane proceeds extreme-
or 100–225 equiv. of iron
the case of blank experiments (Table 1). After the in- sion to anthraquinone 6 after 24 h. Reagent 2, how-
dicated time, the catalyst was removed by flash chro- ever, slowly oxidizes anthracene in methanol at room
ACHTUNGTNER(NUNG III) acetate or pyridine in ly slowly and does not show any measurable conver-
AHCTUNGTRENNUNG
matography and the obtained solution was analyzed temperature with a 1% conversion after 1 hour and
by GC-MS to determine the conversion of aromatic 74% conversion after 24 h (entries 1 and 2). It should
hydrocarbons or adamantane. According to the GC- be noted, however, that more reactive oxidant 2 leads
MS and NMR data, iodobenzene resulting from the to formation of two reaction products after 24 h. The
reduction of hypervalent iodine reagents and reaction first one is the expected 9,10-anthraquinone 6, while
products shown in Table 1 were the only products the second one is 1-hydroxy-9,10-anthraquinone 7.
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Binuclear IronACHTUNGTRENNUNG(III) Phthalocyanine(m-Oxodimer)-Catalyzed Oxygenation
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The addition of 0.10–0.15 mol equiv of Fe
ACHTUNGERTN(NUNG III)-phtha- the reaction temperature results in formation of 17 as
locyanines 3 and 4 leads to a significant increase in the major reaction product.
the reaction rate with a 100% conversion reached in
Finally, both catalysts 3 and 4 are not very effective
2–5 h for catalyst 3 and 2 h for catalyst 4 at room tem- in oxidation of the adamantane into 1-adamantanol
perature (entries 7–10). In the case of catalyst 3 and (entries 24–27) at 25 and 08C.
catalyst 4/oxidant 1 combination (entries 7–9) the
only reaction product observed in GC-MS was 9,10-
antraquinone, while in the case of catalyst 4/oxidant 2 Conclusions
combination, 15% of the 1-hydroxy-9,10-antraquinone
was observed in the reaction mixture, suggesting that In summary, the results of our study show that oligo-
catalyst 4 can further oxygenate a less reactive (as meric iodosylbenzene sulfate 2/complex 4 combina-
compared to anthracene) 9,10-anthraquinone. Lower- tion is an efficient oxygenating pair in the biomimetic
ing the reaction temperature leads to a slightly slower catalytic oxidation of aromatic hydrocarbons. New
conversion rate of the reaction in the presence of asymmetric m-oxodimer 4 is a significantly more pow-
phthalocyanine 4 but expectedly results in a smaller erful catalyst as compared to the well-known m-oxo-
amount of overoxidized product 7 (entry 11). Since dimer 3 and can catalyze the oxidation of various aro-
catalysts 3 and 4 degrade during catalytic oxidation matic substrates.
reactions, and catalyst 4 has basic pyridine fragments
in its core, the oxidation of the anthracene into an-
thraquinone was tested in the absence of catalysts but Experimental Section
in the presence of pyridine (225 equiv.) or FeACTHNUTRGENUG(N III) salt
(100 equiv., entries 3–6). In both cases inhibition of General Methods
the oxidation reaction was clearly observed.
All reactions were performed under a dry nitrogen atmos-
In agreement with our previous reports, the data
presented in Table 1 clearly indicate that the oligo-
meric iodosylbenzene sulfate 2 is the best oxidant, sig-
nificantly more reactive than the commonly used io-
dosylbenzene and thus this oxidant was used for the
oxidation of the other aromatic compounds presented
in Table 1.
The oxidation of the more sterically crowded 2-tert-
butylanthracene 8 is indicative of the superiority of
catalyst 4 (entries 12 and 13). Indeed, with catalyst 3,
100% conversion of 8 into 2-tert-butyl-9,10-anthraqui-
none can be achieved after 20 h (isolated yield is
72%), while complete oxidation of 8 with catalyst 4
was completed after 30 min. Similar to the oxidation
of anthracene, small amounts of two additional over-
oxidation products 10 and 11 were observed in the re-
action mixture (entry 13).
phere with flame-dried glassware. All commercial reagents
were ACS reagent grade and used without further purifica-
tion. Toluene and dichloromethane were distilled from
CaH2 and stored over molecular sieves. Catalyst 3,[9] iodosyl-
benzene sulfate 2[8,10] and iodosylbenzene[2a] were prepared
by known methods. GC-MS analysis was carried out with an
HP 5890 A Gas Chromatograph using a 5970 Series mass se-
lective detector. The APCI-MS experiment was conducted
using a Finnegan LCQ LC-MS system. NMR spectra were
recorded on a Varian INOVA instrument with 500 MHz fre-
quency for protons. Chemical shifts are reported in parts per
million and referenced to TMS as an internal standard. UV-
vis spectra were collected on Jasco V-730 spectrophoto-
meres. MCD spectra were acquired on OLIS DCM-17
system with 1.4T DeSa permanent magnet.
Preparation of Catalyst 4
The preparation of catalyst 4 is shown in Scheme 1. The
asymmetrical metal-free phthalocyanine precursor was syn-
thesized according to the previously reported procedure.[11]
Selected data for this compound are: APCI-MS: m/z=684
[M+1]+ 100%; UV-vis (CHCl3): l=342, 605, 634, 659,
685 nm.
The reasonable oxidation of 2-methylnaphthalene
12 to provitamin K can also be achieved only with the
more active catalyst 4 (entries 14–17). Formation of
three quinone products 13–15 was observed at 25 and
08C. In the reaction at room temperature, the over-
oxidized quinone 15 is the major reaction product
The preparation of m-oxodimer from the asymmetrical
(entries 15 and 17), while lowering the reaction tem- metal-free precursor was achieved by the reaction between
0.54 g (0.79 mmol, 1 equiv.) of metal-free phthalocyanine
and 1.37 g (7.9 mmol, 10 equiv.) of iron(II) acetate in 5 mL
of boiling N,N-dimethyl ethanolamine for 8 h under an
argon atmosphere. After this period of time, the reaction
mixture was poured into water saturated with sodium chlo-
ride and the reaction product was filtered. The target com-
plex 4 was purified using basic alumina (Sorbent Technolo-
gies, Act. 1, 50–200 mm). First, toluene was used as the
eluent to remove reaction impurities and unreacted asym-
metrical metal-free phthalocyanine. After this, the target m-
perature to 08C leads to formation of the target qui-
none 13 as the major reaction product (entry 16).
Catalyst 3 is also not effective in the oxidation of
phenanthrene into 5,6-phenanthrenedione 17 at room
temperature (entries 18 and 19), while use of catalyst
4 leads to formation of the products 17–19, which
were isolated and characterized by NMR spectrosco-
py (entries 20–23). Expectedly, longer reaction times
for room temperature oxidations favor overoxidation
products 18 and 19 (entries 20, 21, 23), while lowering oxodimer 4 was eluted by pure methanol. The methanol was
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Heather M. Neu et al.
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Figure 3. UV-vis (top) and MCD (bottom) spectra of iron-
AHCTUNGTRENN(GUN III) phthalocyanine-(m-oxodimer) 4.
with stirring, at the temperature indicated in Table 1. Sam-
ples of the reaction mixture (100 mL) were collected every
30 min, filtered through 2–3 cm of silica gel suspended in a
Pasteur pipet, washed with a mixture of ethyl acetate and
hexane (2:3 v:v), and then analyzed using GC-MS.
Catalytic Oxidation of Phenantrene
A solution of phenanthrene (25 mg, 0.140 mmol) in metha-
nol (25 mL) was mixed with catalyst 4 (31 mg, 0.02 mmol)
and the oxidant 2 (208 mg, 0.281 mmol) at room tempera-
ture. The reaction mixture (100 mL samples) was analyzed
using GC-MS every 30 min. Upon completion of the reac-
tion, the reaction mixture was concentrated and products
were separated using a TLC plate and ethyl acetate/hexane
(2:3 v:v) mixture as the eluent. Reaction products were col-
Scheme 1. Synthetic pathway for preparation of the iron
phthalocyanine-(m-oxodimer) 4.
ACHTUNGTNER(NUNG III)
evaporated under reduced pressure and the product was fi-
nally purified by washing with hexane and recrystallization
from methanol/hexane.; yield: 31%; UV-Vis and MCD spec-
tra of 4 are shown in Figure 3, while its APCI-mass spec-
trum is presented in Figure 4. Selected data for this com-
pound are: UV-Vis (toluene): l (log e)=358 (4.83), 560 sh,
633 sh, 667 sh, 700 nm (4.9); ACPI-MS: m/z=1491 [M+1]+
100%, 1522 [M+CH3OH]+ 50%, 1554 [M+2CH3OH]+.
The presence of one or two methanol molecules in 4 was
further confirmed by an APCI MS/MS method on the 1554
[M+2CH3OH]+ peak; IR (KBr): n=3068 (Ar-H), 2958
(CH3), 2925 (CH3), 2856 (CH3), 2364, 2345, 1609, 1500,
1482, 1388, 1364, 1327, 1257, 1197, 1082, 1027, 923, 900, 840,
750, 692 cmÀ1.
1
lected as separate fractions and analyzed by GC-MS, H and
COSY NMR methods.
Phenanthrene-9,10-dione: Yield: 1.2 mg (4.1%); GC-MS:
1
m/z=208 (M)+; H NMR (500 MHz, CDCl3): d=8.21 (d, J=
7.5 Hz, 1.5 Hz, 2H), 8.02 (d, J=8 Hz, 2H), 7.73 (t, J=
7.5 Hz, 1.5 Hz, 2H), 7.48 (t, J=8 Hz, 2H).
4-Hydroxyphenanthrene-9,10-dione:
Yield:
10.7 mg
(34%); GC-MS: m/z=224 (M)+; 1H NMR (500 MHz,
CDCl3): d=7.93 (d, J=7 Hz, 1H), 7.87 (d, J=5.5 Hz,
2.5 Hz, 2H), 7.79 (d, J=7.5 Hz, 1.5 Hz, 1H), 7.64 (t, J=
7.5 Hz, 1.5 Hz, 1H), 7.47 (t, J=8 Hz, 1.5 Hz, 1H), 7.40 (t,
J=7 Hz, 2H).
Phenanthrene-4,9,10-triol: Yield: 3.9 mg (12.3%); GC-
1
MS: m/z=226 (M)+; H NMR (500 MHz, CDCl3): d=7.83
(m, 4H), 7.50 (d, J=7.5 Hz, 1H), 7.3 (m, 2H).
Typical Procedure for Catalytic Oxidation of
Aromatic Hydrocarbons
Acknowledgements
A
solution of the appropriate hydrocarbon (0.056–
0.070 mmol) in toluene or methanol (5–10 mL) was mixed
with the amount of the catalyst 3 or 4 shown in Table 1 and
the hypervalent iodine oxidant 1 or 2 (4.5–12 equiv. of O),
This work was supported by a research grant from the Na-
tional Science Foundation (grant CHE-0702734) and Petrole-
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Binuclear IronACHTUNGTRENNUNG(III) Phthalocyanine(m-Oxodimer)-Catalyzed Oxygenation
FULL PAPERS
Figure 4. APCI MS of the ironACTHNUGRTENUNG(III) phthalocyanine-(m-oxodimer) 4.
um Research Fund, administered by the American Chemical
Society (grant PRF-45510-GB-3).
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