Applications of Microwave in Organic Synthesis: An Improved One-step Synthesis of Metallophthalocyanines and a New Modified Microwave Oven for Dry Reaction.

Didier Villemin ^a*, Mohamed Hammadi ^b, Messaoud Hachemi ^b and Nathalie Bar ^a

a) Ecole Nationale Supérieure d'Ingénieurs de Caen (ISMRA), Université de Caen, UMR CNRS 6507, 6 Boulevard du Marechal Juin F-14050 Caen Cedex, France. E mail : didier.villemin@ismra.unicaen.fr

b) Université Boumerdès, Faculté des Sciences de l'Ingénieur, Boumerdès 35000 (Algérie).

Received: 8 September 2001 / Uploaded 10 September 2001

Abstract : Metallophthalocyanine complexes are obtained quickly and efficiently by the reaction of phthalodinitrile with hydrated metallic salts without solvent and under microwave irradiation. The use of a modified commercial microwave oven to perform this type of reactions under dry conditions was described. Metallophthalocyanines and metallododecachlorophthalocyanines of some divalent metals can be also obtained in presence of phthalic or tetrachlorophthalic anhydrides with hydrated metallic salt and urea under microwave irradiation and without solvent.
Keywords : Phthalocyanine; microwave; complexes.

Introduction

Metallophthalocyanine complexes (PcM) are colouring materials which present high thermal stability, light fastness, and inertness to acids and alkalis. They have been studied in details for many years especially with regard to their properties as pigments for printing inks and for plastics [1] and in paints and coatings. Today, phthalocyanine chemistry is undergoing a renewal interest. In fact, phthalocyanines and many of their derivatives exhibit noteworthy properties for applications in material science [2]. For example, phthalocyanines are used in laser-beam printers and photocopiers [3], in non linear optics [4], as liquid crystals [5], as photosensitizers [6], in optical data storage [7], as gas sensors [8], as electrochromic substances [9] and as carrier generation materials in near infrared (NIR) [10]. Many substituted derivatives of phthalocyanines behave like active components in various redox processes, for example, in photoredox reactions and photooxidations in solution [2,11,12] and for photodynamic cancer therapy [2,13,14].

We have previously reported the formation of metallophthalocyanines under microwave irradiation [15]. Recently, we have also described the preparation of metallophthalocyanines on clay, on zirconium phosphate and encapsulated in zeolite. These materials have been used as redox catalyst in organic synthesis [16]. Herein, we described the detailed work and investigation of the synthesis of metallophthalocyanines.

Results and Discussion

Microwave dielectric heating effects are used increasingly in organometallic synthesis [17]. One of the main limitations of the use of microwave ovens for synthesis can be attributed to the difficulties encountered in using organic solvent. In some cases it is possible to conduct the reaction without solvent under dry conditions as we described many years ago. This methodology is now very well established  and we have performed many reactions without solvent under microwave irradiation [16]. In this paper, we described the synthesis of metallophthalocyanines from phthalodinitrile and from phthalic anhydrides as starting materials.

Synthesis of metallophthalocyanines from phthalodinitrile

Linstead and co-workers [18, 21d] have first described the synthesis of metallophthalocyanines by heating a metallic salt with phthalodinitrile in high boiling solvent. This reaction was used for the synthesis of phthalocyanine pigments like copper phthalocyanine in industry.

In the beginning of our study, we have used a commercial multimode microwave oven and we have performed reactions without solvent in an open device in order to avoid the problems associated with the use of organic solvent under microwave like overpressure and inflammability. The formation of phthalocyanine needs a powerfully activation (high temperature). This fact is not a limitation because metallophthalocyanines are thermally very stable. Metallophthalocyanines were obtained by direct reaction of phthalodinitrile with hydrated metallic salt without solvent under microwave irradiation at 2450 MHz (Scheme 1). It is not really a dry reaction because water is necessary to obtain at the beginning of the reaction a strong coupling with microwave. Water allows also the diffusion of the metallic salt and plays also a role in the redox process of formation of metallophthalocyanine. The melted phase allows also the diffusion of the necessary salt for the course of reaction and thus so that phthalodinitrile can be used in excess. In some cases, ammonium formate (8 to 6 eq./ metal) must be added for promotion of the reduction of metal in the salt (Mo) or for keeping the reaction under non oxidative condition (La, Ce). The excess of phthalodinitrile and the free phthalocyanine formed were easily extracted after reaction by washing the product with an organic solvent such as acetonitrile. The quantity of free phthalocyanine formed is generally very low : the infrared of raw reaction mixture showed no characteristic infrared band corresponding to free phthalocyanine (H₂Pc) (no band at 1336, 1322, 750 and 700 cm-1).

Yields of metallophthalocyanine based of the metal salt were quasi-quantitative (95-100%). Transition metals gave easily metallophthalocyanines which are identified by their spectral data (electronic and IR spectra) and their microanalysis.

Although many of phthalocyanines were prepared with a commercial multimode oven, we found that this type of commercial oven is generally not well adapted to obtain reproducible results. So we chose to work with a modified commercial multimode oven or an industrial resonance cavity. With an aim of comparison, the synthesis of copper phthalocyanine was selected like model.

First, we have worked with a commercial multimode microwave oven (Toshiba ER 7620; power max 630W). The use of domestic oven have many limitations on account of multimode cavity is calculated for irradiation of large recipient and a sequential irradiation with full power is used. In this case, some experimental problems were encountered due to the mixture of reactants and an nonuniform distribution of microwave irradiation.

In order to solve these problems, we have built a modified commercial microwave oven (Daewoo DMR 502, power 480W ) in which the sample is mixed during the irradiation in order to homogenise the irradiation and to mix the reactants. This microwave oven use a rotary evaporator, with indented flask heated by a multimode cavity. The modified apparatus (scheme 1) is a rotary evaporator built up on a commercial microwave oven. The reactional mixture was put in a round-bottomed indented flask shaker fitted with a frit on its top in order to prevent the solid drawing. The conduit was protected with a metallic wire mesh connected to the oven mass to avoid microwave leakage's. It is possible to conduct experiment under controlled atmosphere like nitrogen. The mixture of reactant are very efficiently mixed by the indented flask and a glass frit is put to support powder solid in the flask.
 
 

The microwave were produced by a universal generator MES. With a small sample, we have used a monomode resonance cavity TE013 at 2450 MHz, working power 80 W max. The reaction was conducted in quartz tube and the solid is mixed by mechanical agitation.

Choice of mode of irradiation in the formation of Pc(Cu)

In a typical experiment, phthalodinitrile (10 mmol) and hydrated salt (2.5 mmol) were thoroughly mixed. The mixture was irradiated under microwave (table 1) under three different modes of irradiation and the results obtained are reported in table 1.

It must be noticed that with a commercial multimode oven, the results depend upon the quantity of product, they were very difficult to reproduce when the reactions are conducted with small samples (less than 5 g). With large samples the results are poor and need a powerful irradiation. The best results were obtained with the modified microwave oven.
 
 

Table 1 : Synthesis of Pc (Cu) from phthalodinitrile (10 mmol) and Cu Cl2, 2 H2O

Their main advantages are:

- a best repartition and uniformity of microwave irradiation

- a mixing of solid reactants during the activation with microwave irradiation.

- possibility to work under controlled atmosphere (nitrogen) and to prevent hot points.

With small samples (less than 5 g) reproducible results were obtained only by the use of a resonance cavity

Synthesis of metallophthalocyanines from phthalic anhydrides

Metallophthalocyanines are often prepared in industry by more available phthalic anhydrides, by heating a mixture of metallic salt, phthalic anhydride in presence of urea as source of nitrogen. Generally a molybdenum salt like ammonium molybdenate (VI) [Mo7O24(NH4)6,4 H2O] was added in order to catalyse the reaction. The formation of phthalocyanine [15,18] which needs a powerful irradiation is not easier than that obtained with phthalodinitrile. Sometimes addition of small quantity of water was necessary due to the poor coupling of anhydride with microwave. Reduction of metallic salt by urea during the process conduct to formation of metal particles and some arcing were observed during the irradiation. Cracking of Pyrex or oven quartz tube during irradiation can be observed. The reaction needs a powerful microwave intensity due to the poor adsorbing of microwave radiation by the acid. In practice, the commercial microwave oven can be used, a complex mixture of product was obtained with a bad yield of metallophthalocyanines (0-20%) after many purification. The yield can be increased by the use of a modified oven, however the best yield is obtained only with the use of a resonance cavity where an efficient mixing of reactants during the reaction is observed.

This reaction is particularly interesting for the synthesis of substituted phthalocyanines because substituted phthalodinitriles are generally not commercially available contrary to the substituted phthalic anhydrides. We have illustrated this usefulness with the synthesis of hexachlorophthalocyanine an interesting class of phthalocyanines which are very resistant to oxidation. The reaction was not general and we did not obtain success in the case of hexafluorophthalocyanine from tetrafluorophthalic anhydride. With mellitic anhydride, we obtain a similar substance to that prepared by Marvel [19], which is a mixture of polymeric phthalocyanines which can be useful as organic conductors.

In conclusion, this new synthesis of phthalocyanines is rapid and efficient and allow the synthesis of a large range of metallophthalocyanine complexes.

The use of a modified oven allows reproducible synthesis of large quantity of phthalocyanines. The synthesis of small quantity of phthalocyanines needs the use of a focussed microwave cavity.

Synthesis of phthalocyanines from phthalodinitriles is easier than from phthalic anhydrides. Ammonium formate can be used when a reduction of nonoxidative conditions were required. Formation of metal particles can cause the cracking of the tube of irradiation in presence of excess of reducing (ammonium formate or urea in phthalic process).

Experimental

Visible spectra (l max log (e)) in 1-chloronaphtalene (characteristic bands between 6000-7000Å) were obtained with spectrophotometer Perkin Elmer Lambda 15.

Infrared spectra were recorded on Perkin Elmer 684 IR spectrophotometer in KBr with absorptions in cm-1.The infrared showed no free phthalocyanine (H2Pc) (no band at 1336, 1322, 750 and 700 cm-1) and no presence of phthalodinitrile.

Satisfactory microanalytical data (C, H) have been obtained for all metallophthalocyanine (Pc[M]) described in this paper.

Activation by microwave was conducted with a commercial microwave oven (multimode) Toshiba ER 7620; power max 630W (A), or a modified multimode microwave oven (Daewoo DMR 502, power 480W) (B). A monomode resonance cavity TE013 at 2450 MHz working with 800 W max.(C) The microwaves were produced by a universal generator MES 73-800 (Micro-ondes Energie Systèmes (MES), 2 avenue de la Cerisaie, P307, F-94266 Fresnes, France).

Complexes of 18 different metals were prepared (Mg, Zn, Cd, Cu, Ni, Pd, Pt, Co, Fe, Ru, Rh, Ti, Cr, Mn, V, Mo, UO2, Eu) with the commercial microwave oven. We have also prepared some complexes with the modified microwave oven and with the resonance cavity. A comparison with the first method was established.

General procedure

1) Irradiation with a commercial multimode microwave oven (A)

A mixture of phthalodinitrile (10 mmol., 1.28 g) and hydrated metallic salt (2.5 mmol.) finely ground was placed in a 25 ml flask. The solid was then irradiated under microwaves (630 W) for five to fifteen minutes. The solid was washed successively with water (15 mL), acetone (15 mL) and dichloromethane (15 mL) and then was dried under reduced pressure. The solid was extracted by soxhlet extraction for eight hours with acetonitrile as solvent. After drying at 110 °C, the pure phthalocyanine was analyzed.

2) Irradiation with a modified multimode microwave oven (B)

A mixture of phthalodinitrile (20 mmol., 2.56 g) and hydrated metallic salt (5 mmol.) finely ground was placed in a 50mL flask shaker. Ammonium formate (20 mmol) was added in the case of a reducing medium. Water were added (0.5 mL) to the reactional mixture in the case of dry salts without coordinating water. The mixture was mixed and irradiated for five minutes (power 480 W).The product obtained was submitted to the same procedure as previously.

3) Irradiation in a resonance cavity (focused irradiation) (C)

A mixture of hydrated metallic salt (5 mmol.) and phthalodinitrile (10 mmol., 2.56 g) was placed in a quartz tube (diameter 8 mm) under nitrogen flux. The tube was put in the electric field of the cavity TE013 and the microwave absorbed power was set at 80 W for five minutes of irradiation. The product obtained was subjected to the same procedure as before.

Magnesium (II) phthalocyanine [Pc(Mg)][20]

The product obtained as green solid from MgCl2 : [P = 560 W, t = 5 min, A]; C32H16N8Mg; yield : 89%; RN [1661-03-6]; visible spectra : 6776 (3.57); 6447 (2.69); 6115 (2.78); 5835(2.30) ;IR : 3103, 3078 (nC-H), 3042 (nC-H), 1654, 1590, 1572, 1508 (nC-C), 1484 (nC-N), 1446, 1296 (nC-C), 1248, 1228, 1206, 966, 908 (gC-H), 806, 770, 706 (gC-H), 562, 526, 474 (fC-C).

Copper (II) phthalocyanine [Pc(Cu)][21]

The product obtained as blue product from CuCl2 [P = 560 W, t = 10 min, A]; C32H16Cu N8; yield : 92%; RN [147-14-83] ; visible spectra : 6799 (3.88); 6402 (3.30); 6122 (3.39); 5810 (3.19); 5625 (3.08); IR : 3105, 3079 (nC-H), 3041 (nC-H), 1656, 1589, 1572, 1508 (nC-C), 1484 (nC-N), 1446, 1296 (nC-C), 1227, 1205, 1120, 1091, 1050 (b C-H), 965, 909 (gC-H), 806, 770, 730, 705 (gC-H), 663, 563, 525, 473 (fC-C).

Zinc (II) phthalocyanine [Pc(Zn)][22]

The product obtained as green solid from ZnCl2 [P = 490 W, t = 5 min, A]; C32H16N8Zn; yield : 87%; RN [14320-04-8]; visible spectra : 6766 (3.84); 6482 (3.10); 6107 (3.13); 5858 (1.16);IR : 3104, 3082 (nC-H), 1656, 1589, 1571, 1509 (nC-C), 1472 (nC-N), 1446, 1228, 1054 (bC-H), 903 (gC-H), 768, 716 (gC-H), 562, 526, 473 (fC-C).

Cadmium (II) phthalocyanine [Pc(Cd)][23]

The product obtained as blue solid from CdCl2 : [P = 630 W, t = 10 min, A]; C32H16CdN8; yield : 88%; visible spectra : 6988 (3.78); 6767 (4.16); 6458 (3.48); 6104 (3.45); 5811(1.77); IR : 3106, 3078 (nC-H), 3042 (nC-H), 1654, 1590, 1572, 1484 (nC-N), 1446, 1296 (nC-C), 1248, 1228, 1206, 966, 908 (gC-H), 806, 770, 706 (gC-H), 664, 562, 526, 474 (fC-C).

Titanium (III) phthalocyanine chloride [Pc(Ti)Cl][24]

The product obtained as green solid from TiCl3 : [P = 630 W, t = 10 min, A].C32H16ClTiN8; yield : 86%; visible spectra : 6940 (4.30); 6820 (4.29); 6447 (3.55); 6270 (3.64); 6141.(3.50); IR : 3106, 3078 (nC-H), 3042 (nC-H), 1656, 1590, 1572, 1526 (nC-C), 1484 (nC-N), 1446, 1288 (nC-C), 1228, 1206, 1118, 1054 (bC-H), 966, 908 (gC-H), 806, 770, 706 (gC-H), 562, 526, 474 (fC-C).

Zirconyl phthalocyanine [Pc(ZrO)][25]

The product obtained as green solid from ZrOCl2 : [P = 630 W, t = 15 min, A], C32H16N8OZr; yield : 89%; visible spectra : 6950 (4.38); 6637 (4.08); 6321(3.87); 6167 (3.77); 6952 (3.61); 5691 (3.25); IR : 3106, 3079 (nC-H), 3041 (nC-H), 1649, 1589, 1528 (nC-C), 1484 (nC-N), 1446, 1362, 1308 (nC-C), 1228, 1208, 1090, 1054 (bC-H), 966, 770, 716 (gC-H), 640, 561, 526, 473 (fC-C).

Vanadyl phthalocyanine [Pc(VO)][26]

The product obtained as blue-green solid from VOCl3 : [P = 560 W, t = 10 min, A], C32H16N8OV; yield : 81%; RN [13930-88-6]; visible 7003 (4.42); 6658 (3.67); 6312 (3.69); 6023 (3.22); 5811 (1.84); IR : 3106, 3080 (nC-H), 3043 (nC-H), 3043, 1654, 1590 (nC-C), 1484 (nC-N), 1446, 1329, 1288, 1208, 1120 (bC-H), 1018, 966, 806, 770, 704 (gC-H), 526, 473 (fC-C).

Molybdenyl phthalocyanine [Pc(MoO)][27]

The product obtained as blue -violet solid from Mo7O24 (NH4)6, 4 H2O : [P =630 W, t = 4 min, A]; C32H16MoON8; yield : 83%; visible spectra : 7069 (3.77); 6717 (1.68); 6360 (1.72); 6070 (1.51); 5388 (2.60);IR : 3060 (nC-H), 1642, 1608, 1573 (nC-C), 1474 (nC-N), 1406, 1286 (nC-C), 1118, 1088, 1064 (bC-H), 1028 (bC-H), 972, 912, 894, 858 (gC-H), 780, 726 (gC-H), 622, 570, 506, 468 (fC-C).

Manganese (II) phthalocyanine [Pc(Mn)][28]

The product obtained as grey solid from Mn (OCOCH3)2 [P = 560 W, t = 10 min, A], C32H16MnN8; yield : 90%; RN [14325-24-7]; visible spectra : 7262 (4.38); 6788 (3.98); 6494 (3.78); 6091 (3.48); 5740 (3.28); 5180 (3.77);IR : 3106, 3080 (nC-H), 3042 (nC-H), 1644, 1572 (nC-C), 1484 (nC-N), 1414, 1296 (nC-C), 1228, 1122, 1028 (bC-H), 968, 906, 862 (gC-H), 770, 725 (gC-H), 662, 526, 474

Ferrous phthalocyanine[Pc(Fe)][29]

The product obtained as brown solid from (NH4)2 Fe (SO4)2 : [P = 630 W, t = 10 min, A]; C32H16FeN8 ; yield : 87%; RN [132-16-1]; visible spectra : 6941 (3.59); 6602 (3.79); 5976 (3.52); 5276 (3.65);IR : 3106, 3078 (nC-H), 1654, 1572 (nC-C), 1478 (nC-N), 1424, 1288 (nC-C), 1124, 1025 (bC-H), 907, 879, 857 (g C-H), 770, 724 (gC-H), 646, 576, 526, 474 (fC-C).

Ferric phthalocyanine chloride [Pc(Fe)Cl][29]

The product obtained as brown solid from FeCl3 : (A) [P = 490 W, t = 3 min, A]; (C32H16ClFeN8; yield : 79%; RN [132-16-1]; visible spectra : 6559 (4.08); 5976 (3.28); 5641 (2.98); 5205 (3.39).

Ruthenium phthalocyanine chloride [Pc(Ru)Cl][30]

The product obtained as blue solid from RuCl3, 3 H2O : [P= 630 W, t = 3 min, A], (C32H16ClN8Ru ; yield : 91%; visible spectra : 6515 (4.02); 600 (3.72); 5745 (3.63); 5075 (3.55); IR : 3102, 3080 (n C-H), 3036 (nC-H), 1642, 1590, 1572 (nC-C), 1482 (nC-N), 1440, 1290 (nC-C), 1228, 1206, 1102, 1064 (bC-H), 1008, 964, 908, 891, 768, 724 (gC-H), 646, 571, 526, 474 (fC-C).

Nickel (II) phthalocyanine [Pc(Ni)][31]

The product obtained as green solid from NiCl2 : [P = 560 W, t = 10 min, A]; (C32H16N8Ni ; yield : 78%; RN [14055-02-8]; visible spectra : 7679 (3.06); 6694 (4.00); 6447 (3.29); 6030 (3.36); 5670 (2.98); IR : 3102, 3078 (nC-H), 3042 (n C-H), 1643, 1599, 1572 (nC-C), 1484 (nC-N), 1414, 1296 (nC-C), 1228, 1208, 1089, 1031(bC-H), 966, 895, 857 (gC-H), 772, 570, 528, 474 (fC-C).

Palladium (II) phthalocyanine [Pc(Pd)][32]

The product obtained as blue solid from PdCl2 : [P = 630 W, t = 10 min, A]; (C32H16N8Pd ; yield : 65%; visible spectra : 7058 (2.98); 6610 (3.85); 6329 (3.15); 5969 (3.21);IR : 3102, 3080 (nC-H), 3040 (nC-H), 1676, 1590, 1572 (nC-C), 1484 (nC-N), 1412, 1296 (nC-C), 1228, 1208, 1124, 966, 928, 843 (gC-H), 770, 662, 572, 526, 474 (fC-C).

Platinum (II) phthalocyanine [Pc(Pt)][33]

The product obtained as green solid from K2PtCl4 : [P = 560 W, t = 10 min, A]; (C32H16N8Pt; yield : 78%; visible spectra : 6941 (2.74); 6498 (3.57); 6258 (3.09); 5875 (3.10); IR : 3106, 3080 (nC-H), 3042 (nC-H), 1656, 1590, 1572 (nC-C), 1484 (nC-N), 1412, 1298 (nC-C), 1228, 1206, 1127, 1043 (bC-H), 966, 928, 867 (gC-H), 770, 664, 574, 526, 474 (fC-C).

Cobalt (II) phthalocyanine [Pc(Co)][34]

The product obtained as violet solid from CoCl2, 6 H2O : [P = 560 W, t = 10 min, A]; (C32H16CoN8 ; yield : 91%; RN [3317-67-7]; visible spectra : 6698 (4.47); 6400 (3.94); 6043 (3.85); IR : 3079 (nC-H), 3040 (nC-H), 1657, 1609 (nC-C), 1469 (nC-N), 1425, 1288 (nC-C), 1052 (bC-H), 913, 868 (gC-H), 805, 772, 722 (gC-H), 572, 517, 473 (fC-C).

Rhodium (III)phthalocyanine chloride [Pc(Rh)Cl][35]

The product obtained as blue-green solid from RhCl3, 3 H2O [P = 490 W, t = 5 min, A]; (C32H16ClN8Rh ; yield : 87%; visible spectra : 6549 (4.15); 6282 (3.51); 5907 (3.56); IR : 3100, 3082 (nC-H), 3036 (nC-H), 1664, 1618 (nC-C), 1482 (nC-N), 1454, 1298 (n C-C), 1228, 1206, 1076 (bC-H), 966, 916, 882 (gC-H), 768, 704 (gC-H) 664, 560, 526, 474 (fC-C).

Europium (II) phthalocyanine [Pc(Eu)][36]

The product obtained as green solid from Eu2O3 [P = 630 W, t = 15 min, A]; (C32H16EuN8O ; yield : 77%; visible spectra : 6929 (3.96); 6754 (4.14); 6352 (3.76); 6098 (3.79); IR:3 080 (n C-H), 3037 (nC-H), 1590 (nC-C), 1484 (n C-N), 1452, 1296 (nC-C), 1228, 1206, 1054 (bC-H), 966, 912, 870 (gC-H), 806, 770, 706 (gC-H), 560, 526, 474 (fC-C).

Uranyl phthalocyanine [Pc(UO][37]

The product obtained as brown solid from UO2 (C2H4O2)2 , 2 H2O : [P = 630 W, t = 5 min, A];

(C32H16N8UO2 ; yield : 91%; visible spectra : 6977 (3.45); 6776 (3.41); 6642 (3.47); 6329 (3.91); 6094 (3.83); IR : 3106, 3080 (n C-H), 3042 (nC-H), 1642, 1590 (nC-C), 1484 (nC-N), 1452, 1298 (nC-C), 1228, 1206, 1054 (bC-H) 964, 916, 806, 770, 705 (gC-H), 684, 562, 526, 474 (fC-C).

Lanthane (III) phthalocyanine chloride [Pc(La)Cl][38]

The product obtained as a green solid was formed from LaCl3 and HCO2NH4 (6 eq). C32 H16ClLaN8; yield : 87 %; visible spectra : 6976 (3.88); 6637 (3.57); 6353 (3.29);6053 (3.09); IR : 3138, 3024 (nC-H) 1575 (nC-C) 1426, 1088 (bC-H), 966, 780, 706 (gC-H), 668, 582, 526, 474 (fC-C).

Chromium (II) phthalocyanine[Pc(Cr)][39]

The product obtained as green solid from Cr03 and HCO2NH4 (8 eq), C32 H16CrN8; yield : 92 %;visible spectra : 6842 (4.42); 6629 (4.83); 6299 (4.18); 6063 (3.99); 5730 (3.63); IR : 3106, 3078 (nC-H), 3042 (nC-H), 1684, 1610, 1560 (nC-C), 1488 (n C-N), 1448, 1298 (n C-C), 1234, 1058 (bC-H), 942, 893, 856 (gC-H), 814, 756, 718(gC-H), 688, 548, 526, 472 (fC-C).

Cerium (III) phthalocyanine chloride [Pc(Ce)Cl][40]

The product as a green solid was formed from CeCl3, 7 H2O and HCO2NH4 ( 8 eq). C32 H16CeClN8; yield : 90 %; visible spectra : 7017 (3.77); 6851 (3.96); 6619 (3.51); 6198 (3.22); IR : 3142, 3080 (nC-H), 3042 (n C-H), 1576 (nC-C), 1484 (nC-N), 1428, 1228, 1206, 1088 (bC-H), 966, 780, 706 (gC-H), 670, 526, 473 (fC-C).

From phthalic anhydride

General procedure.

The mixture composed with tetrachlorophthalic anhydride (10 mmol) and urea (20 mmol) was ground in a mortar in presence of Mo7O24(NH4)6,4 H2O (0.1 mmol), then the metallic salt (5mmol.) was added. The reactional mixture was put in a tube and was activated under microwave in a resonance cavity (C). The final product was taken again with HCl 1N (50 mL) then neutralised with soda 1N (50 mL) and washed with water. The solid dried at 110°C was purified by soxhlet extraction with acetonitrile as solvent for eight hours. The phthalocyanine obtained was identified with spectroscopic methods.

From phthalic anhydride:

The following phthalocyanines were obtained from phthalic anhydride: Pc(Cu); Pc(Co); Pc (MoO) 93%, ( P=560W, t= 5min., C)

From tetrachlorophthalic anhydride:

Iron III Phthalocyanine chloride [Cl16Pc(FeCl)][29]

The product obtained as green solid from tetrachlorophthalic anhydride (17 mmol; 4. 81 g) and FeCl3 (0.83 g),C32Cl17FeN8; [P= 420 W, t = 2 min, C), yield : 86 %;visible spectra : 685, 4; 656, 4; 611, 7; IR : 1664, 1610 (n C-C), 1558 (nC-C),1436 (nC-C), 1264, 1214, 1192, 1134, 1098 , 954, 930, 768 (n C-Cl), 738, 668, 648, 590 (nC-Cl ), 510, 470 (f C-C).

Cobalt (II) phthalocyanine chloride[Cl16Pc(Co)][34]

The product obtained as green solid from the tetrachlorophthalic anhydride (17 mmol; 4.81 g) and CoCl2, 6 H2O (0. 93 g), C32Cl16CoN8; [P = 620 W, temps = 2 min, C), yield 92 %;visible spectra : 698.1; 667.9; 642.0; 640.0; 604.3; IR : 1676, 1610 (nC-C), 1430 (nC-C), 1272, 1212, 1192, 1132, 1098, 928, 898, 816, 768 (nC-Cl), 736, 658, 592 (nC-Cl ), 532, 468 (fC-C).

Phthalocyanitocopper chloride [Cl16Pc(Cu)][21]

The product obtained as blue-green solid from the tetrachlorophthalic anhydride (17 mmol, 4.81 g) and CuCl2, 2 H2O (0.85 g), C32Cl16CuN8, [P = 620 W, t = 4 min, C), yield 93 %; visible spectra: 707.9; 668.2; 652.3; 603. 2; 583.4; IR : 1611 (nC-C), 1495, 1392 (nC-C), 1275 (nC-C), 1212, 1194, 1097, 948, 928, 805, 768 (nC-Cl), 657, 620, 591 (nC-Cl ), 510.

From tetrafluorophthalic anhydride:

Under similar conditions, no phthalocyanine was obtained with CuCl2, CoCl2 or MnCl2.

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