Supported metalated phthalocyanine as catalyst for oxidation by molecular oxygen. Synthesis of quinones and carbonyl compounds

Article abstract of DOI:10.1081/SCC-120004139

Supported metalated phthalocyanine on K1O or on lamellar zirconium phosphate catalyses the oxidation of hydroquinones (and phenols) into quinones. Some interesting natural napthoquinones were also prepared (Juglone, Menadione, Lawsone, Phthiocol). Supported metalated phthalocyanine was also used in re-oxidation by oxygen of palladium and ruthenium, in the Wacker oxidation of olefins into ketones, in the oxidation of cyclohexadiene and in oxidation of benzylic alcohols in aldehydes.

Full text of DOI:10.1081/SCC-120004139

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SUPPORTED METALATED PHTHALOCYANINE AS CATALYST
FOR OXIDATION BY MOLECULAR OXYGEN. SYNTHESIS OF
QUINONES AND CARBONYL COMPOUNDS
a
b
b
Didier Villemin , Mohamed Hammadi & Messaoud Hachemi
a
Université de Caen, Ecole Nationale Supérieure d’Ingénieurs de Caen, ISMRA, CNRS UMR
507, Caen, F-14050, France
6
b
Université de Boumerdès, Faculté des Sciences, Boumerdes, 35000, Algérie
Published online: 12 Dec 2006.
To cite this article: Didier Villemin , Mohamed Hammadi & Messaoud Hachemi (2002) SUPPORTED METALATED
PHTHALOCYANINE AS CATALYST FOR OXIDATION BY MOLECULAR OXYGEN. SYNTHESIS OF QUINONES AND CARBONYL
COMPOUNDS, Synthetic Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry,
32:10, 1501-1515, DOI: 10.1081/SCC-120004139
To link to this article: http://dx.doi.org/10.1081/SCC-120004139
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SYNTHETIC COMMUNICATIONS, 32(10), 1501–1515 (2002)
SUPPORTED METALATED
PHTHALOCYANINE AS CATALYST FOR
OXIDATION BY MOLECULAR OXYGEN.
SYNTHESIS OF QUINONES AND
CARBONYL COMPOUNDS
1
,
1,2
Didier Villemin, * Mohamed Hammadi,
1
,2
and Messaoud Hachemi
1
Ecole Nationale Supe
ISMRA, CNRS UMR 6507, Universite
F-14050, Caen, France
de Boumerdes, Faculte
5000 Boumerdes, Alge
rieure d’Ingenieurs de Caen,
´ ´
´
de Caen,
2
Universite
´
`
´
des Sciences,
´
rie
3
ABSTRACT
Supported metalated phthalocyanine on K10 or on lamellar
zirconium phosphate catalyses the oxidation of hydro-
quinones (and phenols) into quinones. Some interesting natu-
ral napthoquinones were also prepared (Juglone, Menadione,
Lawsone, Phthiocol). Supported metalated phthalocyanine
was also used in re-oxidation by oxygen of palladium and
ruthenium, in the Wacker oxidation of olefins into ketones,
in the oxidation of cyclohexadiene and in oxidation of
benzylic alcohols in aldehydes.
*
Corresponding author. E-mail: didier.villemin@ismra.fr
1
501
Copyright & 2002 by Marcel Dekker, Inc.
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1
502
VILLEMIN, HAMMADI, AND HACHEMI
The oxidation of phenols into quinones is a reaction of synthetic
interest. The phenol oxidation products are used for the synthesis of natural
products such as vitamins and their intermediates. Concerning the oxidation
of phenols or hydroquinones into quinones, numerous oxidants were
1
2
described in the literature such as chromic oxide, silver oxide, and ceric
3
ammonium nitrate. However, only few reactions use air or oxygen as the
oxidant. On economic and ecological grounds, there is an increasing need
for the development of soft processes, without toxic salts and which do not
4
necessitate high temperature or high pressure. Our attention was focused
on the synthesis of new types of solid catalysts and their applications in soft
oxidation in fine chemistry.
5
Phthalocyanines on different inorganic supports like silica, alumina,
6
7
8
9
zeolite, titanium oxide, or coal, were described as redox catalysts. We
1
0
have shown that the microwave irradiation at 2450 MHz of a mixture of
metallic hydrated salt and phthalonitrile conducted quantitatively to the
metalated phthalocyanine. The reaction of phthalonitrile with a montmor-
illonite K10 or a zirconium phosphate exchanged by metallic ions under
microwave irradiation allows a fast preparation of metalated phthalocya-
nines supported on the layers of these inorganic solids. In the same way, it
was also possible to use a zeolite (LSY-52 and 13X) in order to prepare
metalated phthalocyanine encapsulated in the pores of the zeolites. The
1
1
formed materials were identical to those obtained by classical conditions
but the pores of zeolite do not allow the use of such catalyst in fine
chemistry.
It was shown that the phthalocyanines in solution catalysed the
1
2
oxidation of the hydroquinone into quinone by oxygen. Herein, we have
been interested by the aerobic oxidation of phenols catalysed by supported
metalated phthalocyanine on lamellar solids.
Oxidation of Hydroquinones (and Phenols) in Quinones
In a preliminary study, we have tested the oxidation of hydroquinone
into quinone by air catalysed by a metalated phthalocyanine (Pc [M]) on the
sheet of a montmorillonite K10 or zirconium phosphate (ZP). Hydro-
quinone was easily oxidised at room temperature in quinone by using
PcFe/K10 and air (1 atm), as indicated in Scheme 1. The reaction can be
generalised to substituted hydroquinones obtained from substituted phenols
1
3
by an Elb reaction; they were easily oxidised at room temperature in
quinone by using PcFe/K10 and air (0.5 to 2 h).
Results obtained from different phenols were reported in Table 1.

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SUPPORTED METALATED PHTHALOCYANINE
1503
Scheme 1. Oxidation of hydroquinones.
Table 1. Oxidation of Hydroquinone into Quinone with Supported
Metalated Phthalocyanines
Hydroquinones
Catalysts
Quinones
Yield (%)
98
Pc[Fe]/K10
(
1a)
(2a)
Pc[Co]/K10
Pc[Co]/K10
Pc[Fe]/K10
Pc[Fe]/ZP
95
90
89
94
(
1b)
(
2b)
(
1c)
(2c)
(1d)
(2d)
(
1e)
(2e)

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1
504
VILLEMIN, HAMMADI, AND HACHEMI
Whatever the nature of the support of metalated phthalocyanine
montmorillonite K10 or a zirconium phosphate (ZrPO )], and whatever
[
4
the metal (Fe, Co, Mn) of the phthalocyanine tested, the reactions of oxida-
tion of hydroquinones were quasi similar. The direct oxidation of phenols
with oxygen in presence of supported metal phthalocyanines as oxidant
generally gave quinone at room temperature, but the reaction is very slow
and not selective.
We have also tested this type of reaction in naphthoquinone series.
Many of naphthoquinones are natural products with interesting biological
properties. The 1,4-dihydroxynaphthalene and the 1-naphthol have been
transformed in naphthoquinone with the yield of 96% (1 h) and 65%
(
18 h), respectively, according to the Scheme 2.
Scheme 2. Synthesis of naphthoquinone.
The catalytic system PcFe/K10, in presence of pure oxygen, oxidises
easily the 1,5-dihydroxynaphthalene in 5-hydroxynaphthoquinone or
1
4
Juglone (79% yield). The latter is used as an alimentary stain for soft
drinks. The total oxidation was about 6 h (Scheme 3) at room temperature.
Scheme 3. Synthesis of Juglone.
The 1,3-dihydroxynaphtalene was oxidised in the same conditions in 2-
hydroxynaphthoquinone (or Lawsone) (80% yield) as shown in Scheme 4.
The latter is a natural colouring extracted from Henna (Lawsonia-lythraces)
1
5
used like protective sun.

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SUPPORTED METALATED PHTHALOCYANINE
1505
Scheme 4. Synthesis of Lawsone.
1
Menadione, which is the vitamin K3 carrier, was obtained (yield
5
80% after 70 min) also by catalytic oxidation with Pe[Fe]/ZrPO in the
4
presense of pure oxygen from 2-methyl-1,4-dihydroxynaphthalene, accord-
ing to Scheme 5.
Scheme 5. Synthesis of Menadione.
Menadione treated with acetic anhydride in the presence of triflic acid
1
6
converts into the methyl triacetoxynaphtalene. This ester is saponified by
KOH, oxidised by the air in presence of K10/Pc Fe and has given the
1
antibiotic Phthiocol (75% yield after 20 min), according the Scheme 6.
7
Scheme 6. Synthesis of Phthiocol.
Reoxidation of Transition Metal Catalysts
We have shown that the phthalocyanines supported on the montmo-
rillonite K10 or on zirconium phosphate catalysed the oxidation of the

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506
VILLEMIN, HAMMADI, AND HACHEMI
hydroquinone into quinone by the air at ambient temperature. The oxida-
tion was quantitative whatever the nature of the support: montmorillonite,
or zirconium phosphate, and whatever the metal (Fe, Co, Mn) of the phtha-
1
2,18
locyanine tested. Ba
¨
ckvall
has used the quinone/hydroquinone system in
solution for re-oxidation of the palladium and the ruthenium in selected
three step reversible electron transfer processes under aerobic conditions.
Therefore we have tested the system of heterogeneous hydroquinone/
K10Pc[M] (M ¼ Fe, Mn) in the presence of oxygen as a re-oxidant of palla-
dium and ruthenium. This triple catalytic system was applied to three prin-
cipal types of reactions:
(
i) oxidation of terminal olefins to ketones (Wacker oxidation);
ii) diacetoxylation of cyclic olefins;
iii) oxidation of benzilic alcohols.
(
(
Oxidation of Terminal Alkenes
We have applied the method developed by Ba
1
ckvall et al. to the
8
¨
oxidation in a solution of terminal alkenes to ketones for our heterogeneous
catalyst. For this, we have used the ferrous phthalocyanine intercalated in
zirconium phosphate as catalyst for the aerobic oxidation of hydroquinone
to quinone. This one-pot triple catalytic system was indicated in the Wacker
process described in Scheme 7.
Scheme 7. Catalytic cycle of Wacker oxidation.
There is an electron transfer from the substrate to Pd(II) giving Pd (0),
followed by another electron transfer from Pd (0) to quinone. The hydro-
quinone thus formed transfers an electron to the oxidised form of the metal
macrocycle, which is reduced. The latter is deoxidised by electron transfer by
an oxygen molecule.
The results obtained with Pc[Fe]\ZrPO were reported in Table 2.
4

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SUPPORTED METALATED PHTHALOCYANINE
1507
Table 2. Oxidation of Olefin with PdCl /Pc[Fe]\ZrPO /O
2
2
4
Conversion/
Selectivity
Alkenes
Catalyst
PdCl2
Ketones
Dodecene
1-Hexadecene
Cyclododecene
2-Dodecanone
2-Hexadecanone
Cyclododecanone
82/78
82/75
85/83
PdCl
PdCl
2
2
Oxidation of Allylic and Benzylic Alcohols
In similar fashion, benzylic alcohol was oxidised into benzaldehyde
1
9
using the ruthenium complex RuCl (PPh )
2
and the ferrous phthalo-
3 3
cyanine intercalated in zirconium phosphate in presence of oxygen. The
tripley catalysed reaction is illustrated by Scheme 8. The conversion was
almost quantitative (90–98%).
Scheme 8. Catalytic cycles of oxidation of benzylic alcohol.
Diacetoxylation of 1,3-Cyclohexadiene
Allylic oxidation under homogeneous conditions was described by
1
8
¨
Backvall. We have studied the allylic oxidation of 1,3-cyclohexadiene
into 1,4-diacetoxy-2-cyclohexene under heterogeneous conditions with
Pc[Fe]/ZrPO as a catalyst for the re-oxidation of quinone. The 1,4-diace-
4
toxy-2-cyclohexene was isolated (50% yield).
In all cases, the supported metalated phthalocyanine was active as a
free metalated phthalocyanine. The exact role of the support was not
studied. The supported metalated phthalocyanine could be recovered by
centrifugation of the reactive mixture. The activity of supported metalated
phthalocyanine was preserved.

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508
VILLEMIN, HAMMADI, AND HACHEMI
EXPERIMENTAL
Proton NMR spectra (PMR) were determined on a Brucker AC 250
ꢀ
(
250 MHz, CDCl , Me Si). Melting points (M.p.) in C were uncorrected.
4
3
Visible and ultraviolet spectra were performed on a Perkin-Elmer Lambda
5UV spectrometer. IR spectra were run with a 16PC FT-IR. Microwave
irradiation was carried out with a commercial microwave oven (Toshiba ER
1
7
8
620) at 2450 MHz and with resonance cavity TEO13 joined to a MES 73-
00 generator of microwaves. Mass spectra were carried out on a Nermag
Riber R10; TLC analyses were performed by using Kieselgel Schleicher and
Schull F 1500 LS 254 and Merck 60 F 254. The grinding of the products
were carried out on a analytical grinder A 10 of Janke and Kenkel-IKA
Labortechnik.
The montmorillonite K10 was obtained from the firm of Sud Chemie
¨
and the zirconium phosphate from the firm BDH. The tris(triphenyl-
phosphine) ruthenium (II) chloride [RuCl (PPh ) ] was prepared according
2
3 3
1
9
to the literature.
nQ
Preparation of Montmorillonite K10 Exchanged by M
In a 250 ml flask, the montmorillonite K10 (8 g) was added to a solu-
tion of metallic salt (0.1 mol) [(NH ) Fe(SO ) , CoCl or Mn(OCOCH ) ]
4
2
4 2
2
3 2
dissolved in 100 ml of distilled water. The reactional mixture was
stirred for 24 h at room temperature. The suspension was washed twice
with distilled water then centrifuged. The montmorillonite exchanged by
nþ
M
was washed with methanol and re-centrifuged. The solid was dried
for 24 h in vacuum then finely ground. The final product was a clear beige
colour.
nQ
Preparation of Zirconium Phosphate (ZrPO ) Exchanged by M
4
A 250 ml flask containing 5 g of zirconium phosphate dissolved in
5 ml of distilled water was added to a solution (0.1 mol) of metallic salt
100 ml). The mixture was stirred for 3 h then left standing for 2 h. After
2
(
having decanted the solution, the operation was repeated four times with a
successive change of the ferric solution. The solid was washed two times
with distilled water (100 ml) then with methanol. After centrifugation, the
solid was dried for 24 h in a vacuum.

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SUPPORTED METALATED PHTHALOCYANINE
Preparation of Zeolites Exchanged by M
1509
nþ
3
þ
The zeolites LZY-52 and 13 X have been exchanged by Fe according
to the same experimental procedure to that of zirconium phosphate.
Phthalocyanines Intercalated in the K10 and in the
Zirconium Phosphate
General procedure: A solution of phthalonitrile (10 mmol, 1.28 g) dis-
solved in 10 ml of dichloromethane was added to the solid (ZrPO or K10;
4
2.5 g) exchanged with some metallic cations. After contact for 1.5 h, the
remaining liquid was evaporated under reduced pressure. The activation
of the solid under microwave irradiation (P ¼ power, t ¼ time of irradiation)
was carried out in a resonance cavity. After cooling, the solid was succes-
sively washed with water, acetone (15 ml) and then with dichloromethane
(
15 ml). The solid was dried under reduced pressure and then extracted with
acetonitrile as a solvent using a Soxhlet for 8 h. Catalysts were characterised
by FT-IR, electronic spectra, Debye-Schere RX and elemental analysis.
Electronic spectra of metalated phthalocyanine intercalated into montmor-
illonite or zirconium phosphate was very close to those observed with pure
metalated phthalocyanine, but the bands were shifted.
3
Q
Pc [Fe ] Supported on K 10: [P ¼ 540 W, t ¼ 10 min]. UV–Visible lmax
log(e)/(1-chloronaphthalene): 6988 (3.37); 6626 (3.41); 5976 (3.22). IR (KBr)
cm : 3436, 1632, 1580, 1526, 1442, 1366, 1044, 798, 524.
ꢁ1
3
Q
Pc [Fe ] Supported on ZrPO : [P ¼ 540 W, t ¼ 10 min]. l
log(e)/
1-chloronaphthalene): 6980 (3.45); 6632 (3.48); 6352 (3.18); 6023 (3.05). IR
4
max
(
(
ꢁ
1
KBr) cm : 3446, 1648, 1564, 1526, 1444, 1400, 1056, 766, 516.
2
Q
Pc[Co ] Supported on K10: [P ¼ 490 W, t ¼ 10 min]. UV–Visible lmax
log(e)/(1-chloronaphthalene): 6695 (4.42); 6421 (3.88); 6042 (3.78); 5800
ꢁ
1
3.22). IR (KBr) cm : 1636, 1522, 1400, 1044, 796, 756, 732, 525, 466.
(
2
Q
Pc[Co ] Supported on ZrPO : [P ¼ 480 W, t ¼ 10 min]. UV–Visible
4
lmax log (e/(1-chloronaphthalene): 6712 (4.31); 6376 (3.91); 6072 (3.69);
ꢁ1
5
505 (2.95). IR (KBr) cm : 1654, 1560, 1508, 1490, 1400, 1054, 800, 732, 528
2
Q
Pc[Mn ] Supported on K10: [P ¼ 630 W, t ¼ 10 min]. UV–Visible l
max
log(e)/(1-chloronaphthalene): 7287 (4.29); 6782 (3.97); 6491 (3.81); 5374
ꢁ
1
3.35). IR (KBr) cm : 1582, 1420, 1293, 1044, 967, 910, 870, 781, 738, 533.
(
2
Q
Pc[Mn ] Supported on ZrPO : [P ¼ 630 W, t ¼ 10 min]. UV–Visible
4
lmax log (e)/(1-chloronaphthalene): 6976 (4.37); 6635 (3.99); 6352 (3.41); 6035
ꢁ
1
3.27). IR (KBr) cm : 1581, 1418, 1297, 1044, 965, 908, 872, 779, 738, 534.
(
2
Q
Pc[Co ] Supported on LZY-52: [P ¼ 630 W, t ¼ 20 min]. UV–Visible
lmax log (e/(1-chloronaphthalene): 7807 (2.63); 7343 (2.85); 6697 (4.02); 6003

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1
510
VILLEMIN, HAMMADI, AND HACHEMI
ꢁ
1
(
1
3.68); 5810 (3.29). IR (KBr) cm : 1698, 1684, 1636, 1576, 1570, 1522, 1490,
472, 1404, 1009, 788, 720, 668, 580, 454.
2
Q
Pc[Co ] Supported on 13 X: [P ¼ 630 W, t ¼ 20 min]. UV–Visible l
max
log(e)/(1-chloronaphthalene): 6690 (4.39); 6001 (3.44); 5827(3.08). IR (KBr)
cm : 1697, 1682, 1636, 1577, 1489, 1472, 1406, 1011, 722, 581, 454.
ꢁ
1
2
Q
Pc[Fe ] Supported on LZY-52: Prepared by impregnation with a
solution ferrocene in acetone [P ¼ 630 W, t ¼ 20 min]. UV-Visible lmax
log(e)/(1-chloronaphthalene): 6975 (3.63); 6635 (3.87); 6330 (3.41); 5998
ꢁ1
(
3.34). IR (KBr) cm : 3474, 1644, 1569, 1404, 1278, 1024, 790, 580.
2
Q
Pe[Fe ] Supported on 13 X: Prepared by impregnation with a solution
ferrocene in acetone [P ¼ 630 W, t ¼ 20 min]. UV-Visible l log(e)/
max
(1-chloronaphthalene): 6981 (3.58); 6634 (3.91); 6331 (3.35); 6012 (3.26).
IR (KBr) cm : 3482, 1664, 1566, 1406, 1048, 978, 752, 672, 562.
ꢁ
1
Hydroquinones were prepared by the Elb reaction of phenols. In a
typical experiment, the m-cresol (100 mmol; 10.81 g) was dissolved in
2
00 ml of 10% solution of sodium hydroxide under stirring at room tem-
perature. A saturated aqueous solution of sodium persulfate (100 mmol;
3.8 g) was slowly and carefully added for 3 h. At the end of the addition,
2
stirring was maintained at room temperature. The mixture stood overnight.
The solution was acidified with Congo red and was extracted twice with
ether. The aqueous layer was treated with an excess of hydrochloric acid and
warmed in a steam bath for 30 min. After cooling, it was once again
extracted with ether. The extracted organic layers were combined, dried
on magnesium sulfate and finally distilled to afford the corresponding
hydroquinone.
2-Methylhydroquinone (1b): Yield: 66%, brown solid, m.p. C: 132–133,
C H O , Calcd H 6.5% C 67.73%, Found H 6.61% C 67.62%. NMR H
ꢀ
1
7
8
2
(
7
CDCl ) d 2.22 (s, 3H, CH ); 6.45–6.72 (m, 3H, H arom); 7.18 (s, 1H, OH);
.49 (s, 1H, OH): IR (KBr) cm : 3374 (n OH), 3038, 2978, 1652, 1591,
3
3
ꢁ
1
1490, 1464, 1442, 1282, 1244, 1156, 928, 856, 776.
2,6-Dimethoxylhydroquinone (1d): Prepared from 2,6-dimethoxy-
phenol (104 mmol; 16.21 g) and sodium persulfate (100 mmol; 23.8 g).
ꢀ
Yield: 69%, brown solid, m.p. C: 149, C H O , Calcd H 5.92% C 56.47%,
8
10
4
1
Found H 5.85% C 56.38%. NMR H (CDCl ) d: 3.81 (s, 6H, OCH ); 7.64
s, 1H, H arom); 7.91 (s, 1H, H arom). IR (KBr) cm : 3420 (n OH), 3062,
3
3
ꢁ1
(
2952, 2852, 1696, 1646, 1594, 1482, 1322, 1260, 1220, 1108, 878, 668, 605.
Oxidation to Quinone
General procedure: In a typical experiment, a current of air was passed
through a U tube fitted with a filter flask. The tube contains the supported

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SUPPORTED METALATED PHTHALOCYANINE
1511
phthalocyanine (0.1 g) in suspension in a solution of hydroquinone or
phenol (5 mmol) dissolved in 10 ml of a mixture of dioxane/water (60 : 40)
for 6 h at room temperature. The oxidation of phenol was followed by TLC.
After the disappearance of phenol, the solution was filtered and evaporated
under vacuum. The quinines were purified by chromatography on silica gel
or by sublimation. All products are known compounds and were identified
by comparison of their physical and spectral data with those of authentic
samples. The UV spectra of quinones were carried out in a water–dioxane
mixture.
1,4-Benzoquinone (2a): Yield: 98%, red solid, m.p. C: 111, C H O ,
Calcd H 3.73% C 66.67%, Found Calcd H 3.65% C 66.57%. UV–Visible
ꢀ
6
4
2
lmax log(e) (dioxane/H O, 70 : 30)/nm: 244.4 (4.32), 302.4 (2.48), 433.6
2
ꢁ
1
(
1.31), 4.53 (1.19). IR (KBr) cm : 1684 (nC¼O).
-Methyl-1,4-benzoquinone (2b): Yield: 95%, brown solid, m.p. C:
2–73, C H O , Calcd H 4.95% C 68.85%, Found H 4.87% C 68.73%.
ꢀ
2
7
7
6
2
UV–Visible lmax log(e) (dioxane/H O, 70 : 30)/nm: 278.2 (4.15), 312.3
2
1
(
6
2.75), 422.6 (1.31) NMR H (CDCl ) d: 2.01 (s, 1H, CH ); 6.23 (s, 1H);
3
3
ꢁ
1
.52 (m, 1H); 6.85 (d, 2H). IR (KBr) cm : 1689 (nC¼O).
,6-Dimethylbenzoquinone (2c): Yield: 90%, brown solid, m.p. C: 72,
C H O , Calcd H 5.92% C 70.58%, Found H 6.01% C 70.50%. UV–Visible
ꢀ
2
8
8
2
lmax log(e) (dioxane/H O, 70 : 30)/nm: 270.6 (4.29), 318.1 (2.52), 414.3
2
ꢁ
1
(
1.25). IR (KBr) cm : 1685 (nC¼O).
,6-Dimethoxybenzoquinone (2d): Yield: 89%, brown solid, m.p. C:
52–255, C H O , Calcd H 4.8% C 57.14%, Found H 4.87% C 57.12%.
ꢀ
2
2
8
8
2
UV–Visible lmax log(e) (dioxane/H O, 70 : 30)/nm: 279.5 (4.25), 3.79 (2.69),
2
ꢁ1
4
65.5 (0.45). IR (KBr) cm : 1678 (nC¼O).
,6-Dichlorobenzoquinone (2e): Yield: 94%, brown solid, m.p. C:
18–120, C H O Cl , Calcd H 1.14% C 40.72%, Found H 1.25% C
ꢀ
2
1
4
3
6
2
2
2
0.43%. UV–Visible lmax log(e) (dioxane/H O, 70 : 30)/nm: 277.4 (4.38),
.25 (2.74) 432.6 (1.05). IR (KBr) cm : 1683 (nC¼O), 775 (nC-Cl).
2
ꢁ
1
Naphthoquinone (2f): Product formed by oxidation of 1-naphthol
0.74 g) and from 1,4-dihydroxynaphthalene (0.82 g) both in the presence
(
of PcFe/ZrPO . Yield: 96%, m.p. C: 119–120. C H O , Calcd H 3.82%
ꢀ
4
10
6
2
C 75.94%, Found H 3.78% C 76.0%. UV–Visible lmax log(e) (dioxane/
1
H O)/nm: 205.7(1.23), 256.9 (4.22), 335.3 (3.39). NMR
H (CDCl )
ꢁ
2
3
1
d: 6.89 (s, 2H, CH¼); 7.42–8.23 (m, 4H, H arom.). IR (KBr) cm : 1673
(
nC¼O).
5-Hydroxy-1,4-naphthoquinone (Juglone) (2g): Product formed from
,5-dihydroxynaphthalene in acetone. Yield: 87%, red brick solid,
1
C H O , Calcd H 3.47% C 68.97%, Found H 3.58% C 68.90%. m.p. C:
ꢀ
1
0
6
3
1
62. UV–Visible lmax log(e) (dioxane/H O, 70 : 30)/nm: 249.3 (4.21), 331.1
2
1
(
3.18), 422.1 (2.98). NMR H (CDCl ) d: 6.76 (s, 2H, CH¼); 7.25–7.45
3

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1
512
VILLEMIN, HAMMADI, AND HACHEMI
ꢁ
1
(
(
m, 3H, H arom.). 7.77 (s, 1H, OH). IR (KBr) cm : 3241 (nOH), 1683
nC¼O), 1587, 1170, 884, 535.
2-Hydroxy-1,4-naphthoquinone (Lawsone (2h): Yield 80%, orange
solid. C H O , Calcd H 3.47% C 68.97%, Found H 3.53% C 68.92%.
1
0
6
3
ꢀ
m.p. C: 192. UV–Visible l
(
log(e) (dioxane/H O, 70 : 30)/nm: 276.3
max
2
1
4.48), 334.3 (3.28). NMR H (CDCl ) d: 6.37(s, 1H, OH); 7. 26 (s, 1H, H
3
ꢁ1
arom.); 7.25–8.14 (m, 4H, H arom.). IR (KBr) cm : 3166 (nOH), 1676
nC¼O), 1592, 1170, 874, 668, 536.
-Methyl-1,4-naphthoquinone menadione (2i): Yield: 80%, yellow solid,
(
2
ꢀ
m.p. C: 105–106. C H O , Calcd H 4.38% C 78.25%, Found H 4.42% C
1
1
8
2
7
3
7
1
8.18%. UV–Visible l
32.5 (3.36). NMR H (CDCl ) d: 2.21 (s. 3H, CH ); 6.85 (s, 1H);
log(e) (dioxane/H O, 70 : 30)/nm: 264.1 (4.18),
max
2
1
3
3
ꢁ
1
.75–8.14 (m, 4H, H arom.). IR (KBr) cm : 1732, 1668 (nC¼O), 1593,
082, 940, 884, 720, 650.
2-Hydroxy-3-methyl-1,4-naphthoquinone (phthiocol) (2j): Obtained
from 2-methyl-1,3,4-triacetoxynaphthalene prepared from menadione.
1
6
The 1,2,4-triacetoxy-3-methylnaphthalene (632 mg, 2 mmol), dissolved in
methanol (20 ml) was saponified by addition of sodium methoxide
(
324 mg, 6 mmol) and Pc[Fe]/ZrPO (0.1 g) was added. An air-stream was
4
passed in suspension for 1 h. After filtration and evaporation of methanol,
the phthiocol was crystallised (357mg, 95%). Yellow needles (cyclohexane),
ꢀ
m.p. C: 173–174 (ether þ hexane). C H O , Calcd H 4.29% C 70.21%,
1
1
8
3
ꢁ
1
Found H 4.35% C 70.08%. IR (KBr) cm : 3330 (nOH), 1655 (nC¼O).
1
NMR H (CDCl ) d: 2.08 (s, 3H, CH ); 7.29 (s, 1H, OH); 7.5–8.1 (m, 4H, H
3
3
arom.).
Oxidation of Alkenes to Ketones
General procedure: In a typical experiment, a mixture comprised of the
alkene (5 mmol), palladium chloride (0.2 mmol; 0.35 mg), hydroquinone
(
H O 0.2 ml) was introduced into a U tube. Oxygen (1 atm.; 50 ml min
1 mmol; 110 mg) and Pc[Fe]/ZrPO (1 g) in aqueous DMF (DMF 2 ml,
4
ꢁ
1
)
2
was bubbled through the solution for 3 h at room temperature. The mixture
was centrifuged and methylene chloride (10 ml) was added to the super-
natant. The organic solution was washed with a solution of 3N (10 ml)
and then dried out on magnesium sulfate. The solvent was eliminated
under reduced pressure. Products were identified by comparison of their
retention times (gas chromatography) with authentic samples and purified
by flash chromatography on silica.
2-Dodecanone: Obtained from 1-dodecene (1.10 ml), isolated yield
3%, C H O, Calcd H 13.12% C 78.2%, Found H 13.08% C 78.31%.
5
1
2
24

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SUPPORTED METALATED PHTHALOCYANINE
1513
1
NMR H (CDCl ) d: 0.9 (t, 3H, CH ), 1.25 (m broad, 18H, CH ), 1.95 (s,
3
3
2
3
H, COCH ), 2.2 (t, 2H, CH ).
3
2
2-Hexadecanone: Obtained from 1-hexadecene (1.30 ml), isolated yield
9%, m.p. C: 45. C H O, Calcd H 13.42% C 79.93%, Found H 13.40%
ꢀ
4
1
6
32
1
C 80.06%. NMR H (CDCl ) d: 0.9 (t, 3H, CH ), 1–1.5 (m, 30H, CH ), 2 (s,
3
3
2
3
5
H, COCH ) 2.3 (t, 2H, CH ).
Cyclododecanone: Obtained from cyclododecene (2.5 g), isolated yield
3
2
ꢀ
1%, m.p. C: 60. C H O. Calcd H 12.16% C 79.06%, Found H 12.25%
1
2
22
1
C 78.98%. NMR H (CDCl ) d: 1.5–2.5 (m, broad, CH ). IR (film): 2934,
3
2
2306, 1710 (CO), 1470.
Oxidation of Benzylic Alcohol
The mixture comprised of benzylic alcohol (10 mmol, 1.12 g), tris (tri-
phenylphosphine) ruthenium (II) chloride [RuCl (PPh ) ] (0.4 mmol),
hydroquinone (4 mmol, 220 mg), Pc[Fe]/ZrO4 (1.4 g), DMF (3 ml), and
2
3 3
H O (0.3 ml) was subjected to the same general procedure mentioned above.
2
Benzaldehyde: Obtained from benzyl alcohol, yield GC (95%), isolated
1
ꢁ1
8
7
0%. IR (film) cm : 1708 (nC¼O); 1190; 977 (dC-H). NMR H (CDCl ) d:
3
.1–8.0 (m, 5H, H arom.); 9.9 (s, 1H, CHO).
Furane 2-carboxaldehyde: Obtained from furfuryl alcohol, yield GC
1
(
(
98%), isolated 85%. NMR H (CDCl ) d: 6.7 (dd, 1H), 7.25 (d, 1H), 7.7
3
d, 1H), 9.73 (s, 1H, CHO).
E-Cinnamyladehyde: Obtained from E-cinnamyl alcohol, yield GC
1
(
90%), isolated 77%. H (CDCl ) d: 6.5 (d, 1H, CH), 6.85 (d, 1H, CH);
3
7
.0–7.8 (m, 5H, H arom.); 9.65 (d, 1H, CHO).
E-(2-Furanyl)-3-propen-2-al: Obtained from (2-furanyl)-3-propen-2-ol,
1
yield isolated 75%. NMR H (CDCl ) d: 6.5 (d, 1H, CH), 6.85 (d, 1H, CH);
3
7.0–7.8 (m, 5H, H arom.); 9.75 (d, 1H, CHO).
Diacetoxylation of 1,3-Cyclohexadiene
We added successively in a 50 ml flask, the supported phthalocyanine
Pc[Fe]/ZrPO4 (1 g), Pd(OAc)2 (0.14 mmol, 0.032 g), LiOAc (1.37mmol,
.14 g), the hydroquinone (0.28 mmol, 0.04 g) and, finally, acetic acid
5 ml). Finally the 1,3-cyclohexadiene (1.5 mmol, 120 mg) in hexane (5 ml)
0
(
was added. Oxygen was bubbled through the mixture stirred at room tem-
perature for 24 h. After filtration, the organic layer was recovered. The
aqueous layer was diluted in aqueous saturated solution of sodium chloride
(
3 ml) and then extracted with a solution of hexane/ether (1 : 1) (3 ꢂ 10 ml).

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1
514
VILLEMIN, HAMMADI, AND HACHEMI
The combined organic layers were washed successively with an aqueous
saturated solution of sodium chloride (3 ꢂ 3 ml), with water (3 ꢂ 3 ml) and
with soda 2 M (3 ꢂ 5 ml) and were then dried over magnesium sulfate and
evaporated under reduced pressure.
1,4-Diacetoxy-2-cyclohexene (mixture of trans and cis): Yield isolated
0%, C H O . Calcd H 7.12% C 60.59%, Found H 7.23% C 60.28%. IR
5
(
1
0
ꢁ
14
1
4
1
film) cm : 2926, 1730, 1652, 1436, 1370, 1138, 916. NMR H (CDCl ) d:
3
1
.7–2.21 (m, 6H, CH ); 2.04 (s, 6H, CH ); 5.30 and 5.17(m, 2H, CHOAc);
1
2 3
8
5.9 (m, 2H, CH¼). The product is a mixture of isomers (estimation from
NMR: trans/cis about 9).
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4

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2002 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
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1
Received in the UK February 8, 2001

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