Abstract:
This invention provides a novel process for preparing soluble phthalocyanines by microwave irradiation in the absence of any organic solvent. Three different starting materials, i.e. t-butylphthalic anhydride, t-butyl phthalonitrile and metal-free H 2 Pc (tetra-t-butylphthalocyanine) have been adopted, respectively. The starting material with proper metal compound, such as chloride or acetate were irradiated in a commercial microwave oven for a period of 1 to 30 minutes at a power of 200˜900 W. This process is noted to reduce drastically reaction time of MPc formation from 8˜24 hours to 10˜30 minutes due to its unique heating by microwave irradiation. Sandwiched type MPc 2  (such as Lu Pc 2 ) can be produced only through metal replacement from metal-free phthalocyanine by microwave irradiation.

Description:
BACKGROUND OF THE INVENTION 
     1. Field of the Invention Received 
     The present invention relates to a novel process for preparing soluble phthalocyanines by microwave irradiation in the absence of any organic solvents and represented by the general formula shown in FIG. 1 wherein R is an alkyl group such as t-butyl or an alkoxy group like pentoxy, and Mt is a metal or non-metal, like Co, Ni, Cu, Mg, Al, Pd, Sn, Tb, Lu, Ce, La, Zn, or H. 
     2. Description of the Related Prior Art 
     Phthalocyanines exhibit extremely good stability and photoelectric properties due to its unique chemical structure, and hence have been used widely. They are currently the largest consumed dyes and/or pigments in the world, and play a major role in the application for the high technology industry. 
     Phthalocyanines can be made into a film that in turn can be fabricated into an element by means of a variety of methods. Among those methods, the spin-coating has the lowest cost (1-2) . Films made from phthalocyanines have been applied over various fields such as photo-recording materials (3-4) , gas sensors (5) , electrochromic elements (6) , non-linear optics (NLO) (7)  and photocells (8) . 
     The structural formula of phthalocyanines is given in FIG. 1, wherein R represents alkyl, t-butyl, or an alkoxy group like pentoxy, and Mt represents a central material of metal, like Co, Ni, Cu, Mg, Al, Pd, Sn, Tb, Ce, La, Zn, Lu or a metal-free material like H atom. 
     Microwave was developed from the radar during the Second World War. At that time, it was discovered that microwaves emitted from the radar were capable of drying large ceramic objects. The application of microwaves for the household electric commodities had been, however, since 1970. Nevertheless, in recent years, many studies have been devoted to exploring the feasibility of the application of microwaves on chemical reactions. 
     Microwave is an energy in the form of an electromagnetic wave. It is a non-ionization radiation that can induce the migration of electron and the rotation of dipole moment, and hence cause the motion of a molecule. Microwave heating is different from conventional heating method mostly in its mode of energy delivery. Traditional heating method delivers heat energy by conducting through a container containing the solution, and homogeneously distributes the heat to the solution and hence raising the temperature thereof. On the contrary, microwave heating delivers heat by radiation, and therefore, can heat reactants directly and accordingly promoting its efficiency. 
     Synthesis of phthalocyanine by microwave irradiation was first proposed by Ahmad Shaabani (12)  in 1998 using a phthalic anhydride lacking a side group as the starting material. This method had, however, a disadvantage in that the phthalocyanine synthesized had a poor solubility. It is insoluble in almost every solvent other than concentrated sulfuric acid. In 1999, Cezar Ungurenasu (13)  proposed a process for preparing phthalocyanine by microwave irradiation with phthalonitrile or diiminoisoindoline as the starting material. The product thus prepared had a defined solubility, however, it was disadvantageous in that the solvent must be involved in the reaction, i.e., it was not a dry preparation, and hence contained high production cost. Further, it differed from the scope claimed by the present invention. 
     The traditional syntheses of phthalocyanine, no matter what starting material is used, required a relatively long reaction time and a considerable high energy to provide sufficient kinetic energy to overcome the reaction kinetic barrier and hence, promote the collision probability and energy of molecules, which results in low efficiency. Accordingly, the object of the present invention is to provide a novel process for preparing phthalocyanine by microwave irradiation that can eliminate the above-described disadvantage associated with the traditional process. Consequently, it is possible to shorten the reaction time, and produce soluble phthalocyanines that can be used to fabricate elements by avoiding an expensive vacuum sputtering method, and thus, increasing its industrial practicability. 
    
    
     BRIEF DESCRIPTION OF THE DRAWINGS 
     FIG. 1 is a representation of the prepared phthalocyanine by the general formula wherein R is an alkyl group such as t-butyl or an alkoxy group like pentoxy, and Mt is a metal or non-metal, like Co, Ni, Cu, Mg, Al, Pd, Sn, Tb, Lu, Ce, La, Zn, or H. 
    
    
     SUMMARY OF THE INVENTION 
     Accordingly, the invention provides a novel process for preparing soluble phthalocyanines by microwave irradiation. This process does not require a solvent and thus alleviates heat and increases the collision frequency and effective collision probability of reacting molecules, and hence increases the reaction yield and reaction rate. There are three different kinds of starting materials used for the preparation of soluble metal containing tetra-t-butyl phthalocyanines; (1) t-butyl-phthalic anhydride, (2) t-butyl-phthalonitrile, and (3) metal-free tetra-t-butyl-phthalocyanine H 2 Pc. 
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT 
     The novel process for preparing phthalocyanine according to the invention comprises reacting the starting materials with various metal compounds in the absence of any solvent under microwave irradiation in a microwave oven. Metal chlorides and acetates are used as metal compounds. 
     The starting materials used herein can be any conventional starting material useful for preparing phthalocyanine, for example, phthalic anhydride, phthalonitrile and metal-free phthalocyanine. 
     In the process for preparing phthalocyanine by microwave irradiation, the starting reactants are placed in a heat-resistant quartz vessel of 10 ml. Next, the vessel is placed on the rotation table in the microwave oven. During the microwave irradiation, reactant molecules will have their dipole moments rotating in accordance with the change of the microwave field, and hence, increase collision frequency and effective collision probability, as described above. As a result, the reaction is accelerated and the reaction yield is promoted. 
     Thus, prepared phthalocyanine can be represented by the formula shown in FIG. 1 wherein 
     R is an alkyl group such as t-butyl, or an alkoxy group like pentoxy; 
     Mt is a metal or non-metal, like Co, Ni, Cu, Mg, Al, Pd, Sn, Tb, Lu, Ce, La, Zn, or H atom. 
     The invention will be further illustrated in more detail by the following examples, but not limited by these descriptions. 
     EXAMPLES 
     Five examples are provided for illustrating the preferred embodiment of the novel process according to the invention. The invention is, however, not limited by these examples. Among these, Example 1 uses phthalic anhydride as the starting material; Examples 2 and 3 employ phthalonitrile as the starting materials. The center in the ring of Example 3 is a non-metal H atom. Example 4 and 5 use H 2 Pc as the starting material, whereby the central metal in Example 5 is the rare earth metal Lu, which forms a sandwich type of phthalocyanine that can be identified by mass spectrometry. It should be noted that Lu diphthalocyanine can only be prepared by using H 2 Pc as the starting material. All the examples are reacted in a microwave oven at a power of 200˜900 W for a period of 1 to 30 minutes. 
     Example 1 
     Synthesis of Cu tetra-t-butyl-phthalocyanine using 4-tert-butyl-phthalic anhydride (4 g, 19.6 mmol), copper chloride (0.72 g, 5.45 mmol), urea (48 g, 0.8 mmol), ammonium chloride (4.048 g, 75.7 mmol) and ammonium molybdate (0.44 g, 2.23 mmol) were pulverized in a mortar, placed in a quartz vessel of 50 ml, and irradiated in a microwave oven at 440 W for 15 minutes. Thereafter, the reaction product was rinsed with demonized water, filtered under suction and dried under vacuum at 120° C. 
     500 ml of 2% HCl was added to the dried product and the resulting mixture was heated to boil for several minutes. After filtering and drying, it was added to a 500 ml of 1% aqueous NaOH solution, boiled for several minutes, filtered, and dried. The acid/base washing was repeated several times. The oven-dried crude product was dissolved in dichloromethane, and filtered with suction. The filtrate was concentrated under reduced pressure and dried in a vacuum to yield a bluish solid. The solid was recrystallized from ethanol and dichloromethane (5:1) to obtain Cu phthalocyanine with a yield of 47%. 
     IR(KBr); 2962, 2896, 2855, 1616, 1528, 1484, 1365, 1338, 1256, 1195, 1145, 1082, 1056, 923, 828, 745, 688, 553 cm −1 . MS: m/z 800(M + ). UV-Vis (n-hexane)λ max : 670 nm. 
     Example 2 
     Synthesis of Mg Tetra-t-butyl-phthalocyanine Using 4-Tert-butyl-phthalonitrile 
     4-tert-butyl-phthalonitrile (0.5 g, 2.72 mmol) and magnesium chloride (0.0645 g, 1.36 mmol) were ground homogeneously and the resulting mixture was placed in a quartz vessel. After addition of 5 ml, 1,8-diazabicyclo[5.4.0] undec-7-ene (DBU), the quartz vessel was irradiated in a microwave oven at 440 W for 10 minutes. A mixture of toluene and water (1:2 v/v) was added to precipitate the product. After filtering and drying, the product was Soxhlet extracted with methanol. 0.4380 g of Mg phthalocyanine was obtained. The yield was 85%. 
     IR (KBr); 2954, 1640, 1481, 1441, 1361, 1320, 1253, 1196, 1145, 1081, 1042, 916, 826, 751, 688, 538 cm −1 . MS: m/z 761(M + ). UV-Vis (methanol)λ max : 674 nm. 
     Example 3 
     Synthesis of Central Metal-free Tetra-t-butyl-phthalocyanine Using 4-Tert-butyl-phthalonitrile 
     4-tert-butyl phthalonitrile (0.5 g, 2.72 mmol) was placed in a quartz vessel. After addition of 5 ml DBU, the quartz vessel was irradiated in a microwave oven at 440 W for 10 minutes, and a mixture of toluene and water (1:2 v/v) was added to precipitate the product. After filtering and drying, the product was Soxhlet extracted with methanol. 0.4144 g of central metal-free phthalocyanine (H 2 Pc) was obtained. The yield was 83%. 
     IR (KBr); 2955, 1616, 1456, 1361, 1316, 1254, 1182, 1007, 869, 823, 743, 518 cm −1 . MS: m/z 740 (M + ). UV-Vis (THF)λ max : 673 nm. 
     Example 5 
     Synthesis of Lu Tetra-t-butyl-diphthalocyanine Through Metal Replacement 
     Central metal-free tetra-t-butylphthalonitrile (0.2 g, 0.27 mmol) and lutetium acetate (0.0953 g, 0.27 mmol) were ground homogeneously and the resulting mixture was placed in a quartz vessel. 3 ml of DBU was added to the vessel, and the vessel was irradiated in a microwave oven at 440 W for 10 minutes. A mixture of methanol and water (1:2 v/v) was added to wash the product. After filtering and drying, 0.1581 g of Lu tetra-t-butylphthalocyanine was obtained. The yield was 71%. 
     IR (Kbr): 2956, 1637, 1608, 1482, 1455, 1362, 1315, 1275, 1253, 1223, 1194, 1140, 1077, 1043, 1023, 915, 822, 749, 673, 531, 505 cm −1 . MS: m/z 1649(M + ). UV-Vis (n-hexane)λ max : 676 nm. 
     Spectra of Various Phthalocyanines 
     Table 1 exhibits characteristic absorption peaks in UV/Vis spectra of various mentioned above phthalocyanines obtained in examples mentioned above. Owing to the unique chemical structure, phthalocyanine exhibits specific optical characteristics. From the UV/Vis spectra, it is clear that two main strong absorption regions were present, namely, Q region around 670 nm and B region around 340 nm. Both of the two regions are related to π-π* transition and the resonance on their rings. 
     Table 1. Characteristic absorption peaks in UV/Vis spectra of various lab-made phthalocyanines 
     
       
         
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 1 
               
               
                   
               
               
                 Name 
                 Q region 
                 B region 
                 Name 
                 Q region 
                 B region 
                 Name 
                 Q region 
                 B region 
               
               
                   
               
             
             
               
                 CoPc 
                 664 
                 331 
                 ZnPc 
                 673 
                 337 
                 TbPc 2   
                 684 
                 347 
               
               
                 NiPc 
                 665 
                 332 
                 DyPc 2   
                 675 
                 346 
                 LuPc 2   
                 676 
                 346 
               
               
                 CuPc 
                 670 
                 334 
                 PdPc 
                 657 
                 329 
                 LaPc 2   
                 647 
                 334 
               
               
                 MgPc 
                 674 
                 348 
                 SnPc 
                 684 
                 341 
                 H 2 Pc 
                 696, 659 
                 340 
               
               
                   
               
             
          
         
       
     
     Solubilities of Various Phthalocyanines 
     Table 2 displays a solubility of various lab-made phthalocyanines, wherein: ⊚, soluble (&gt;3 wt. %); ∘, slightly soluble (1 wt. %˜3 wt. %); Δ, hardly soluble (&lt;1 wt. %). 
     
       
         
               
             
           
               
                 TABLE 2 
               
               
                   
               
             
             
               
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
             
          
         
       
     
     The Correlation of Reaction Condition with Yield of Phthalocyanine 
     Table 3 sets forth the reaction condition used in various example and yields of phthalocyanine prepared. 
     
       
         
               
               
               
               
               
             
           
               
                 TABLE 3 
               
               
                   
               
               
                   
                   
                 Microwave 
                 Reaction time 
                 Yield 
               
               
                 Name 
                 Starting material 
                 power (w) 
                 (minute) 
                 (%) 
               
               
                   
               
             
             
               
                 CuPc 
                 t-butyl-phthalic 
                 440 
                 10 
                 47 
               
               
                   
                 anhydride 
               
               
                 MgPc 
                 t-butyl phthalonitrile 
                 440 
                 10 
                 85 
               
               
                 H 2 Pc 
                 t-butyl phthalonitrile 
                 440 
                 10 
                 83 
               
               
                 ZnPc 
                 tetra-t- 
                 440 
                 10 
                 29 
               
               
                   
                 butylphthalocyanine 
               
               
                 LuPc 2   
                 tetra-t- 
                 440 
                 10 
                 71 
               
               
                   
                 butylphthalocyanine 
               
               
                   
                 (H 2 Pc) 
               
               
                   
               
             
          
         
       
     
     ADVANTAGES OF THE INVENTION 
     The invention provides several advantages as follows: 
     1. Due to the unique property of heating associated with microwave irradiation instead of heating in a condition and convection fashion involved in conventional synthesis, undue heat energy consumption can be lowered; 
     2. Since the operation of microwave field may cause dipolar rotation of reacting molecules, and hence increase the collision frequency and the effective collision probability, the reaction time can be reduced drasticaly from 8˜24 hours to 10˜30 minutes and the yield can be raised; 
     3. It can produce a phthalocyanine that is soluble in an organic solvent and can be used to fabricate elements by utilizing the convenient spin-coating method instead of an expensive vacuum sputtering method, and thus increase its industrial practicability; and 
     4. Since no organic solvent is involved in the reaction according to the invention, the disposal of organic waste can be greatly reduced and the impact on the environment can be largely avoided. 
     Many changes and modifications in the above-described embodiment of the invention can, of course, be carried out without departing from the scope thereof. Accordingly, to promote the progress in science and the useful arts, the invention is disclosed and is intended to be limited only by the scope of the appended Claims. 
     REFERENCES 
     1. P. N. Moskalev et al. 1979 , Russian Journal of Inorganic Chemistry , 24, 2, 188. 
     2. K. Takeshita et al. 1991 . Bull. Chem.Soc.Jpn ., 64, 1167. 
     3. P. Kivits et al. 1981 . Applied Physics , A26, 101. 
     4. M. F. Dautartas et al. 1985 , Applied Physics , A36, 71. 
     5. Y. Q. Liu et al. 1998 , Supramolecular Science , 5, 507. 
     6. J. Silver et al. 1997 . IEEE Proc. Circuits Devices Syst ., 144,2, 123. 
     7. Hari Singh Nalwa et al. 1995 . Thin Solid Films , 254, 218. 
     8. K. Petritsch et al. 1999 . Synthetic Metals , 102, 1776. 
     9. S. Caddick. 1995 . Tetrahedron , 51, 10403. 
     10. Andre Loupy et al. 1998 . Synthesis , 1213. 
     11. M. H. Young, et al. 1998 . Chemistry , 56, 4, 269. 
     12. Ahmad Shaabani. 1998 . J. Chem. Research , 672. 
     13. Cezar Ungurenasu. 1999 . Synthesis , 10, 1729.