0000015902 00000 n The reaction products obtained by carrying out the synthesis of metal phthalocyanines in accordance with this invention are recovered conventionally by removing the diluent and impurities and drying usually under vacuum. CD and UV−vis absorption spectroscopy show that these compounds aggregate when dissolved in 75% EtOH−25% CHCl3, but not in 60% EtOH−40% CHCl3. Found inside – Page 882... 797 Materials synthesis by polymerization, 525–534 Matrix stabilization, ... synthesis in W/CO2 microemulsions, 354 Metal phthalocyanine, MP copper or ... Metal phthalocyanines are usually synthesized by either one of two routes. M2PHS.12H20 (where M=Cu(m. Ni(m 0000019807 00000 n 0000001794 00000 n The syntheses of a novel 1,4,8,11,15,18,22,25-octahexyloxy-2,3,9,10,16,17,23,24-octa-(4-trifluoromethoxyphenyl) phthalocyanine (3a) and its zinc(II) phthalocyanine derivative (3b) have been described and characterized by elemental analysis,¹H NMR, 13 C NMR, 19 F NMR, mass, UV-Vis and FT-IR.The newly prepared metal-free phthalocyanine and its zinc(II) counterpart are soluble in most organic . 0000011490 00000 n Dept of Industrial Chemistry, College of Industrial Technology, Nihon University, 1-2‐1 Izumi‐cho, Narashino, Chiba 275 Japan. Request PDF | Metal complexes of tetrakis(2-carboxyphenylsulfanyl)phthalocyanine. Privacy Policy A mixture of 150 parts of tetrachlorophthalic anhydride, 195 parts of urea, 17.8 parts of cupric chloride, 1.6 parts of ammonium molybdate and 400 parts of hexachlorobutadiene was heated slowly with agitation to 190° C., at which temperature the reaction was essentially completed. (1999). The syntheses and characterization of metal‐free and metal‐containing (Zn and Ni) derivatives of a symmetrically octa‐substituted phthalocyanine derived from 4,5:12,13‐bis(4′‐tert‐butylbenzo)‐8,9‐(4″,5″‐dicyanobenzo)‐6,11‐ditosyl‐6,11‐diaza‐2,15‐dithiacyclohexadeca‐4,8,12‐triene and CuPc from 4,5:12,13‐bis(4′‐tert‐butylbenzo)‐8,9‐(4″,5 . The presence of alkaline earth or alkali metals is found to be essential for accelerating the reaction rate for the ammonia synthesis process. Search for more papers by this author. 0000021921 00000 n One‐pot synthesis: A new strategy for direct synthesis of metal phthalocyanine nanocrystals from their precursors is reported based on a chemical reaction in nanosized micelles under UV irradiation. View 0 peer reviews of The synthesis and characterization of a new metal-free phthalocyanine substituted with four diloop macrocyclic moieties on Publons Download Web of Science™ My Research Assistant : Bring the power of the Web of Science to your mobile device, wherever inspiration strikes. Synthesis. 0000009539 00000 n The synthesis, spectral and magnetic susceptibility on symmetrically substituted metal (ΙΙ)-octa-methoxyphenyl imino phthalocyanine by condensing octa amino phthalocyanines with o-anisaldehyde are described. One well-known method for reducing the particle size is the acid pasting technique which involves dissolving the crude in relatively large amounts of sulfuric acid and then reprecipitating the phthalocyanine by rapid dilution with water. This two-volume work combines comprehensive information on the chemistry of the fluorinated heterocycles. & Terms of Use. Copyright © 2018 Elsevier Inc. All rights reserved. Higher yields and shorter reaction times are also realized by carrying out the syntheses in this manner. Synthesis, structures, and properties of crystalline salts with radical anions of metal-containing and metal-free phthalocyanines Chemistry . Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry: Vol. The final chapter deals with a survey of the structure, synthesis, and physiochemical properties of porphyrazines with annulated heterocycles. This book is a valuable resource for research scientists, engineers, and clinicians. 74260) contains 14‒15 chlorine atoms and features exceptionally high resistance to any effects; however, its coloring power is lower than that of Pigment Blue 15 (C.I. 9, pp. and the aliphatic carbon atoms also gave two signals at 31.92 substitution [29]. 74160). 0000002022 00000 n Copyright © 2021 Elsevier B.V. or its licensors or contributors. 4.2 Procedure for synthesising the metal-free phthalocyanine (H 2 PcH 16) Phthalonitrile (0.50 g, 3.9 mmol) was dissolved in n -pentanol (2 ml). The metal-free phthalocyanine (3a) consists of a mixture of deprotonated/free base species in DMF. This monograph describes the preparation, fabrication and structure of phthalocyanine-based materials. The design and synthesis of metal-free and metallo- In the present paper, we describe the synthesis of phthalocyanines has been an area of intense research metal-free and metallophthalocyanines in which activity for over 70 years [1 - 3]. Synthesis, spectral and catalytic properties | Carboxylic acid sodium salts of the phthalocyanine derivatives with . Metal phthalocyanines having a narrow particle size distribution are synthesized via the phthalodinitrile or phthalic anhydride-urea route using hexachlorobutadiene as the diluent. Fused metal phthalocyanine polymers with higher molecular weight were prepared by baking equal molar quantities of pyromellitic dianhydride and phthalic anhydride with urea, ammonium chloride,. 0000011468 00000 n Metal phthalocyanines M 2 (PcTN) 2 Nap (M = Mn 2+, Fe 2+, Co 2+, Cu 2+) were synthesized by using the liquid solvent method . The procedure of Example 1 was repeated except that an equivalent amount of nickel sulfate (Example 2), cobalt chloride (Example 3) or iron chloride (Example 4) was substituted for the cupric oxychloride. However, identification of active sites responsible for the origin of catalytic activity in transition metal phthalocyanine is a dif A modification of this method is described by Tarantino et al. The presence of a catalyst is optional in phthalodinitrile syntheses but is usually preferred in the phthalic anhydride-urea synthesis to assure maximum conversion. The literature survey revealed about the reports on synthesis spectral and magnetic susceptibility on substituted (II) octaamino phthalocyanines. When 100 parts of the dried crude were boiled with 500 parts of 5% caustic soda, 44 parts of purified crude containing 91% of copper phthalocyanine having an organic bonded chlorine content of 3.5% and an organic bonded sulfonic acid (SO3 H) content of 1.5% were obtained. Found inside – Page 727... CN Ph Ph Ph 8 9 10 Phthalocyanines The reaction conditions employed for the synthesis of a phthalocyanine depend on the metal to be inserted as well as ... In the present paper discusses the synthesis and spectral and magnetic susceptibility on substituted metal (II) 1, 3, 8, 10, 15, 17, 22, 24- ocat methoxyphenyl imino phthalocyanines. The Proceedings in this volume are a refereed selection of presentations from The Third Asia-Pacific EPR/ESR Symposium (APES'01), held in Kobe, Japan from October 29 to November 1, 2001. All rights reserved. The application of molecules in technological devices hinges on the proper understanding of their behavior on metallic electrodes or substrates. 0000004292 00000 n Generally sufficient hexachlorobutadiene will be present to provide a suspension which can be agitated easily. The target compounds were synthesized: 15 phthalocyanines from 2,3-dicyanohydroquinone in 3 steps via 1,2-dicyanobenzene-3,6-bis(trifluorate) and 1,2 . Agitation was continued at 190° C. for a total reaction time of 5-6 hours and the resulting melt was dried under vacuum for 4 hours. The newly prepared metal-free phthalocyanine and its zinc(II) counterpart are soluble in most organic . The dried product was 280 parts (80% yield) of crude having a purity of 50%. J. Chem. To prepare these complexes, the phthalocyanine synthesis is conducted in the presence of metal salts. The advantages of the new methods of direct MPcs/MPs synthsis known as electrochemical direct synthesis, the synthesis of the direct interaction of zero valent metals and ligands and oxidative dissolution of metals in nonaqueous media are also under consideration. The metal phthalocyanines are a well-known class of compounds which, in finely divided form, find wide acceptance as pigments. 0000026668 00000 n Metal phthalocyanine oligomers that possess peripheral carboxylic acid groups were prepared by the reaction of pyromellitic dianhydride, a metal salt, urea, and a catalyst. The widely known phthalocyanine dye Pigment Green 7 (C.I. Keiichi Sakamoto. The synthesis of tetra and octa perfluoroalkyl substituted zinc and metal free phthalocyanines (ZnPc and H 2 Pc) are reported.The compounds 1-5 have been prepared by nucleophilic substitution of 4-nitrophthalonitrile with 1H,1H,2H,2H-perfluorooctanethiol, 1H,1H,2H,2H-perfluorodecan-1-ol, 1H,1H-perfluorodecan-1-ol, 1H,1H-perfluorotetradecan-1-ol and 1H,1H-perfluoro-3,6,9-trioxatridecan-1-ol . Conditions for synthesizing unsubstituted phthalocyanine and its metal complexes from phthalonitrile at low temperatures (0-50°C) are optimized. The dried product was 180 parts (90% yield) of crude copper phthalocyanine containing about 6% of bonded chlorine. The syntheses of a novel 1,4,8,11,15,18,22,25-octahexyloxy-2,3,9,10,16,17,23,24-octa-(4-trifluoromethoxyphenyl) phthalocyanine (3a) and its zinc(II) phthalocyanine derivative (3b) have been described and characterized by elemental analysis,¹H NMR, 13 C NMR, 19 F NMR, mass, UV-Vis and FT-IR.The newly prepared metal-free phthalocyanine and its zinc(II) counterpart are soluble in most organic . Metal-free phthalocyanine derivatives have been synthesized in very short times with high yields in the presence of 1,1,3,3-tetramethylguanidinium trifluoroacetate (TMGT) as an ionic liquid or tetrabutylammonium bromide (TBAB) as a phase transfer reagent under both classical heating conditions and using microwave irradiation. Phthalocyanines can be obtained by heating phthalimides or phthalic anhydride with metal salts, hexamethyldisilazane, a catalytic amount of p-TsOH, and DMF at 150 °C. 0000019785 00000 n A modification of the acid pasting technique is known as acid swelling and uses an adjusted amount and concentration of the acid so that actual dissolution does not occur. Soluble metal-free and metal (copper (II), iron (III), and cobalt (II)) phthalocyanine tetracarboxylic acids (5-8) were synthesized using a novel method consisting of improved hydrolysis based . All The obtained Φ F value for this phthalocyanine (3a) is related with the mixture of these two species in DMF. When 200 parts of the crude were purified by boiling with 500 parts of 5% aqueous hydrogen chloride, 110 parts of a purified crude having a phthalogreen content of 90% were obtained. 0000001124 00000 n In addition, high-purity metal phthalocyanine sheet polymers synthesized from compounds. Found insideThe work is primarily organized by methods, but also covers highly relevant complexes, such as metal-polymer coordination compounds. Films of metal phthalocyanines are widely used in chemiresistive sensors towards various gases and volatile organic vapors. The reactions can be carried out as low as 150° C. but it is generally preferred to perform the reaction at about 170° to 200° C. in order to achieve satisfactory yields. The crude can be worked up into a pigment using any of the conventional techniques for particle size reduction but is particularly adapted to the wet or dry grinding procedures. 0000021828 00000 n Found inside – Page 294... synthesis of, 4 metal-free and metal phthalocyanines from, 7 method, synthesis of metal-free phthalocyanines, 9–10 refluxing, 10 Platinum phthalocyanine ... in U.S. Pat. trailer << /Size 85 /Info 46 0 R /Encrypt 49 0 R /Root 48 0 R /Prev 153134 /ID[<301e20972c7a37505957c2a8d1b13bb3><842d5e6fbd5642b41a678c86bd45bada>] >> startxref 0 %%EOF 48 0 obj << /Metadata 45 0 R /Pages 44 0 R /Type /Catalog /PageLabels 42 0 R >> endobj 49 0 obj << /Filter /Standard /R 2 /O ( U�V�.�`�����Dz�-���#_m�_�}�g) /U (��kprԨ�w���.gOLE���b�h|�) /P -4 /V 1 /Length 40 >> endobj 83 0 obj << /S 253 /L 379 /Filter /FlateDecode /Length 84 0 R >> stream A mixture of 150 parts of phthalodinitrile, 40 parts of cupric chloride and 500 parts of hexachlorobutadiene was heated slowly with agitation to 200° C., at which temperature the reaction was completed. They can be used in optical data storage, new solar cells and biomedical sensors. Functional Dyes discusses the synthesis of these new, high-value dyes and pigments as well as their applications and performance. Six metal (Cu, Zn) phthalocyanine dyes bearing bulky benzoic acid groups and chlorine were synthesized and their optimized molecular structures, electrostatic potential surfaces, optical properties, thermal stability, and dispersion properties were determined using computational modeling, UV-Vis spectrometry, TGA, and DLS. This paper. The UV−vis absorption spectra of films of the nickel phthalocyanine are similar to those of solutions of the . Citation: W. M. Darwish , Synthesis of highly soluble fluoro containing metal -phthalocyanines and [hexafluoroisopropylidene]-bridged metal-phthalocyanine polymers, Egypt. 0000017690 00000 n These materials have blue to purple colors with a metallic luster and are soluble in sulfuric acid, dimethylsulfoxide, dimethylformamide, and dimethylacetamide. Thus, pigmentation can be carried out by ball or salt milling in the presence or absence of water or another liquid known to provide a desired crystal form. The UV−vis absorption spectra of films of the nickel phthalocyanine are similar to those of solutions of the . The resulting pigment was a very strong copper phthalocyanine pigment in the beta modification and possessed excellent pigmentary properties. Found inside – Page 138Other metal phthalocyanines including the fluorinated and unsubstituted iron(II) phthalocyanine complexes 13 (R1 = F) and 13 (R1 = H), respectively, ... 0000022012 00000 n 0000014670 00000 n Thus, acid treatment is the preferred technique for converting crude beta into the alpha modification. What we claim and desire to protect by Letters When a second portion of the purified crude in an amount equal to 12 parts was ground and recovered as above except that the grinding medium contained 3 parts of ethoxyethanol and 0.3 part of sodium dichromate as a substitute for the 3.3 parts of aniline and the grinding temperature was 75° C., the resulting product was a red shade alpha copper phthalocyanine pigment having excellent color strength and brilliance. Found inside – Page 182... cyanide is the standard procedure of preparing aryl nitriles, especially for the phthalonitriles used in the synthesis of metal phthalocyanines. Two copper phthalocyanines are shown in the figure below. As regards suitable diluents, Tarantino et al. 0000001367 00000 n In this book, you will find synthesis and some applications of various phthalocyanine derivatives. Large amounts are not detrimental but for reasons of economy are usually not recommended. Although the above acid treatments give pigments of good color strength, the special techniques required for handling and disposing of waste acid make the treatment economically unattractive, particularly in light of modern day quality standards and environmental controls. A hyperbranched phosphorus-containing copper phthalocyanine compound (DOPO-CuPc) was successfully synthesized and used as the flame-retardant additive to prepare flame-retarded epoxy thermosets. 1625-1630. Agitation was continued at 190° C. for a total reaction time of 5-6 hours and the product was recovered as in Example 6. milling beaker half filled with 1-3 mm. When another 12 part portion of the purified crude of this comparison was stirred with 96 parts of concentrated sulfuric acid for 2 hours at 70° C., the resulting mixture drowned in 1500 parts of water at 15° C., and the suspension heated to the boil, filtered and washed with water to neutrality, the resulting product was reddish tint alpha copper phthalocyanine pigment having much less color strength and less brilliance than the alpha form of the pigment of this example. All parts and percentages are by weight unless otherwise indicated. This volume examines the chemistry of natural and synthetic dyes produced for non-textile markets, where much new basic research in color chemistry is now taking place. Found inside – Page 199H- and J-aggregates • Metal phthalocyanines • Photophysical properties ... quaternized mercaptopyridine-substituted zinc-phthalocyanines: Synthesis, ... Thus by the choice of the metal donor which is usually a metal-yielding salt such as the halide or sulfate and preferably a chloride of copper, nickel, zinc and the like and the particular phthalodinitrile- or phthalic anhydride-containing component used in the synthesis, a variety of metal phthalocyanines can be obtained. Highly efficient and very stable iron and/or cobalt-based catalysts for the ammonia synthesis reaction were synthesized by one-step pyrolysis of metal phthalocyanine precursors. Agitation was continued at 200° C. for a total reaction time of 4 hours and the resulting mixture was dried under vacuum for 4 hours. The crude products of these examples were phthaloblue crudes containing 3 and 1% organic bonded chlorine respectively. N-4 macrocycles of phthalocyanine (Pc) are very important dyad-dyes with tinctorial nature and widely used in dye industries.Pc pigment consists of four isoindole units with affinity for coordination to central metal ion (N → M) due to its diverse tetra-dentate coordination properties , , .These giant macrocycles have received considerable attention because of their synthetic . 0000031895 00000 n Download Full PDF Package. Found inside – Page 377Metal phthalocyanines can also be obtained by an electrochemical process . The feasibility of the electrosynthesis of PCM was reported by Yang and Straughan ... A mixture of 150 parts of phthalic anhydride, 290 parts of urea, 21 parts of monosodium-4-chlorophthalate, 15.5 parts of monosulfonated phthalic acid, 25 parts of cupric oxychloride, 8 parts of aluminum oxide, 1.8 parts of ammonium molybdate and 500 parts of hexachlorobutadiene was heated slowly with agitation to 190° C., at which temperature the reaction was almost completed.