pr 2,925,423 Patented Feb. 16, 1960 1. A further object of this invention is to provide prac tical processes for synthesizing compounds of the above S 2,925,423 - formula. Various additional objects and achievements SOLVENTSOLUBLE METAL PATHALOCYANNE of this invention will appear as the description proceeds. COMPOUNDS AND PROCESS OF MAKING THE My preferred process for manufacturing said com nés comprises heating a metal phthalocyanine poly Wiktor Weinmayr, Landenberg, Pay-assignor to E. I. du li-metal salt thereof, or an ester - Pont de Nemours and Company, WiWiig, ibi. r of 1 to 4 Catoms in the alkyl . corporation of Delaware M alocyanine polysulfonyl chloride lyselfonamide, or a nuclear halogen derivative of NoDrawing Applicati any such compound in a mixture of sulfur tetrafluoride . .andhyarogen fluoride in a sealed-vessel, at a temperature of 100° to 175°C., for a convenient length of time, say 1 to 8 hours. said initial phthalocyanine This invention relates to a novel series offraetal m . 2 of those above mentioned, 'phthalocyanine derivatives which are soluble in organic balt. The number of sulfo “solvents such as acetone, alcohol, benzene and pyridine. groups per molectile (using this term to embrace both For simplicity of reference, acetone will be used herein the sulfonic acid radical and its functional derivatives as after as typical of said group of organic solvents, and above specified) is preferably not less than 2 per mole 2a substance will be considered as soluble in this standard, 20 cute. Customarily, however, it will be 3 to 4. if it dissolves therein to the extent-of at least 0.1% by eady indicated, the initial material may be en *weight, although at 20° C. some of the compounds dis of halogen in the nucleus, or it may contain -fcuissed hereinbelow will dissolve to ana extent as high as - 16-in) halogen atoms (F, Clor Br) per mole 10% or even higher. ; cule, in being the number of sulfo groups in the molecule. phthalocyanine,As is well known, nickel metal phthalocya phthalocyanine such as copper av gether, the initial material may be defined by the (II) perature or at it wherein. MPc, in and Xhave the same meaning as in , ) is a perceptib Formula I, the subscript z may have a value from zero to . atives of said compounds, such (16 in): inclusive, while:Z stands for OH, OM1 (M1=an. o, alkoxy, phenyl, phenoxy, ani 3-alkali metal), OR (R=alkyl-of-1 to 4 C-atoms), Clor. fonated copper phthalocyanine is soluble NH. the degree of sulfonation is high enough;but The process; above-outlined not-only, converts the SOZ phthalocya fine derivatives soluble in organic solvents groups into SQF groups, but also tends to introduce have been scarce. fluorine into the Bznuclei. As a consequence, y in the Fn U.S. Paterit 2,227,628, fluorinated copper phthalo 40 final-product (Formula I above) will generally be greater cyanine 'containing up to 7-fluorine atoms permolecule than 2 in the initial material. (Formula II), provided z and polychloropolyfluoro copper phthalocyanines have. is not near-its upper limit of (16 -n). been described. But these compounds are pigments, in Furthermore, where the initial-material has no halo 'soluble in water and in organic solvents. gen-at-all or only a low contentithereof, the product of In the case of chlorinated derivatives, copper phthalo -the-autoclaving treatment-may be subjected to halogena cyanines having various C1 contents, from 0.5 atom (on 45 tion in known manner to introduce additional halogen the average) to 15.5 or even 16 atoms permolecule have: atoms; into the nuclei, which halogen atoms may be been known for a longtime. But in their solubility char chlorine, bromine or more fluorine. - s 'acteristics they are true to the "rule: They are insoluble in Finally, I may treat the initial material-of Formula II water and in organic solvents. , ' , " . 50 above with agents adapted only to replace Z in the group r. This inventionisi based on the amazing discovery that SOZ by fluorine, i.e., without achieving simultaneous 3 metal phthalocyanines icontaining both fluorostilfonyl. fluorination in the ring. If the initial material has no groups and nuclear:halogeni Substituents, there being at nuclear halogen (i.e., z=0, in Formula II), the product least: two SOF groups and at leastCone nuclear halogen of this treatment may be isolated, and then treated with atom: per molecule, are: soluble in organic solvents, as 55 agents adapted to introduce halogen (F, Clor, Br) into typified by a solubility of at least 0.1% by weight in the Bz-rings. A simple illustration of such alternative acetone and often rising to more than 10%. This is true: process is the treatment of copper phthalocyanine tetra particularly where the nuclear halogenis fluorine, chlorine sulfonyl chloride in an autoclave with a solution of potas 3 or bromine. (In other words, it has an atomic number sium fluoride in hydrogen fluoride, recovering the result not exceeding 35) . opper phthalocyanine tetrasulfonyl fluoride and re objectAccordingly, the production this invenition of hoveliconipoun embra asE. its inci al 60 acting upon the... " latter withP . a. desirable. s - halogenating.e. ' agent,- - - .is . suchuch as chlorine, bromine, sulfur monochloride or sulfur expressed by the general formula ... tetrafluoride, in hydrogen fluoride. ... It will be clear from the aforegoing available methods : sor). of synthesis that X in the formula of the product is . not limited to representing a single halogen; instead, it may represent various combinations of Cland F, Brand "wherein-MPc designates the molecule of a metal-phthalo F, or Cl, Brand F, whose total number per molecule . cyanine, M beinga-metal of the group consisting of cop -per, nickel and cobalt, X designates halogen-selected from 70 The quantities of SF, and HF to be employed in my 'preferred process above set forth may vary from 1 to a theis a groupnumeral consisting-of from 2 to 4, fluorine and y ischlorine a numeral and not bromine, less than in preferred10 parts (byprocess weight) above of setSF, forti and from - 0.5- - - to- - - - -50 - - - - parts- ... 2,935,433 - - - - -- . - 3 4. - of HF per part of initial polysulfo metal phthalocyanine. tained was extracted with acetone. Upon evaporation The preferred duration of the heating is best determined of the acetone, 4.9 parts of a fluorinated copper phthalo by experiment and observation of the results. One hour cyanine was obtained. will give a quantity of acetone-soluble product in some Analyses of the new blue dye showed a N:F ratio cases, but a longer period generally increases the yield. of about 1:1. Inasmuch as there are 8 N-atoms per Two to six hour may be taken as an optimum period molecule, and inasmuch as the initial material contained, for most cases. on the average, only about 2.4 sulfo groups per molecule, The theory of the reaction is not altogether clear to and since it appears logical that each SO3Na group is me, and should not be taken in any sense as a limitation converted in the above reaction to SOF, it follows from upon this invention. But for the sake of making the 0. the above analysis that considerable nuclear fluorination understanding thereof clearer, I offer the following as a has taken place, resulting in fact in some 5 to 6 nuclear probable hypothesis for the course of the reaction. F-atoms per molecule... The sulfur tetrafluoride acts on the SOZ groups, con The acetone and benzene solutions of the reaction verting them into SOF groups, and in combination product were blue; sulfuric acid solutions were green. with HF it acts further on the benzene nuclei to replace The product showed also marked solubility in many some of the H-atoms (if such are still available) by other organic solvents. It was also highly resistant to fluorine. oxidation with a hot dilute sulfuric acid-ceric sulfate solu An incidental, equally unexpected, but most valuable tion, whereas the starting material was readily oxidized in property of my novel compounds is that they possess ; this solution at room temperature. The new product increased resistance to oxidation. Thus, whereas copper 20 was also very resistant to oxidation with boiling 95% phthalocyanine and copper phthalocyanine sulfonic acids nitric acid. Upon oxidation with fuming nitric acid, a are readily oxidized by acidic, aqueous, ceric sulfate solu high yield of a sulfonyl fluoride of phthalimide was tions at room temperature, and whereas even polychlo obtained. - rinated copper phthalocyanine containing as high as 14 The fluorinated copper phthalocyanine of this example Cl-atoms per molecule is quickly oxidized by ceric sul 25 did not lose its solubility in organic solvents by heating fate solutions upon slight warming, many of the novel it in 100% sulfuric acid to 130 C. and drowning the compounds of this invention will withstand heating in solution on ice. Neither did it become water- or am boiling ceric sulfate solution (110° C.) for several hours monia-soluble by that treatment. without being changed to any perceptible degree. Example 2 This valuable collateral property makes my novel com pounds useful in many fields where hitherto known Twenty parts of the potassium salt of a copper phthalo phthalocyanine compounds have not been applicable. cyanine tetra(4)sulfonic acid (made from 4-sulfophthalic For instance, inasmuch as the novel compounds of this acid), 60 parts of anhydrous hydrogen fluoride, and 30 invention are not attacked by peroxides, they may be: parts of sulfur tetrafluoride were heated in a nickel bomb incorporated as colorants into monomers which are to be to 150° C. for 6 hours, After isolation of the reaction polymerized by the aid of dibenzoyl peroxide or similar product and extraction with acetone as described in catalysts into plastics.