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

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SUPPORTED METALATED PHTHALOCYANINE AS CATALYST

FOR OXIDATION BY MOLECULAR OXYGEN. SYNTHESIS OF

QUINONES AND CARBONYL COMPOUNDS

a

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.

www.dekker.com

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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

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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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[Fe]/K10

Pc[Fe]/ZP

95

90

89

94

(

1b)

(

2b)

(

1c)

(2c)

(1d)

(2d)

(

1e)

(2e)

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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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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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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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Table 2. Oxidation of Oleﬁn with PdCl /Pc[Fe]\ZrPO /O

2

4

Conversion/

Selectivity

Alkenes

Catalyst

PdCl₂

Ketones

Dodecene

1-Hexadecene

Cyclododecene

2-Dodecanone

2-Hexadecanone

Cyclododecanone

82/78

82/75

85/83

PdCl

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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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 TE_O₁₃joined 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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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 l_m_a_x

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 l_m_a_x

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

l_m_a_xlog (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

l_m_a_xlog (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

l_m_a_xlog (e/(1-chloronaphthalene): 7807 (2.63); 7343 (2.85); 6697 (4.02); 6003

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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 l_m_a_x

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

ꢁ

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

ꢁ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

l_m_a_xlog(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

6

2

UV–Visible l_m_a_xlog(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

ꢁ

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

2

l_m_a_xlog(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

8

2

UV–Visible l_m_a_xlog(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

0.43%. UV–Visible l_m_a_xlog(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 l_m_a_xlog(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 l_m_a_xlog(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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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

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

ꢁ

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

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

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

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

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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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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1515

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1

Received in the UK February 8, 2001

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Article Doi

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

DOI: 10.1081/SCC-120004139

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Article abstract of DOI:10.1081/SCC-120004139

Full text of DOI:10.1081/SCC-120004139

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