PROCESS FOR THE PREPARATION OF SUBSTITUTED AMIDO PHTHALOCYANINE DERIVATIVES AND SUBSTITUTED AMIDO PHTHALOCYANINE DERIVATIVES

Abstract: A process for the preparation of substituted amido phthalocyanines having the general formula (I): MPc-(CONR<1>R<2>)n, via the reaction of a phthalocyanine carboxamide having the formula MPc (CONH2)x wherein Pc is a Phthalocyanine ring; M is a hydrogen or a metal capable of forming a metal phthalocyanine such as Mg, Al, Ni, Fe, Zn, Pb, Sn or Cu and x is a number from 0.1 to 4.0, with an amine acid salt denoted by formula (II), wherein R<1> and R<2> are independently selected from the group consisting of hydrogen; an alkyl group having 1-20 carbons; a cyclic alkyl group; an aryl group; an arylakyl having 1-20 carbons; an alcohol group having 2-20 carbons; an alkyl amino alkyl group; an aliphatic amine having 1-20 carbons; an aliphatic amine acid salt having 1-20 carbons; polyoxyalylene groups ranging in molecular weight 89-2000; polyoxyalkyleneamines ranging in molecular weight 148-4000; Z is the hydrogen sulphate or the hydrochloride salt of the amine.

Description: PROCESS FOR THE PREPARATION OF SUBSTITUTED AMIDO PHTHALOCYANINE DERIVATIVES AND SUBSTITUTED AMIDO PHTHALOCYANINE DERIVATIVES TECHNICAL FIELD The present invention relates to a novel process for the synthesis of substituted amido phthalocyanines and to novel substituted amido phthalocyanine deπvatives BACKGROUND The preparation of substituted amido phthalocyanine deπvatives is well known and is descπbed in GB 844,419 and more recently EP 0519395 The multi-step pπor art process for the production of substituted amido phthalocyanine denvatives start from the well known carboxamide of phthalocyanine The phthalocyanine carboxamide is manufactured from a substituted phthaiic acid deπvative or anhydπde deπvative, namely tπmellitic acid or anhydπde The tπmellitic acid is reacted with phthaiic acid or anhydπde in the presence of urea , copper salt , and ammonium molybdate either in the presence of a high boiling organic solvent such as nitro benzene or ortho nitro toluene , or using excess urea as the solvent for the reaction The ratio of tπmellitic acid and phthaiic acid can vary depending on the desired substitution level of the phthalocyanine carboxamide The reaction mixture is heated at 180- 250° C for approx 4-20 hours The reaction product thus obtained can be further puπfied by dilute aqueous acid wash , or by conventional acid pasting to yield a phthalocyanine carboxamide which is normally 90% pure The next stage of preparation is to hydroiyse the resulting amide to the acid followed by reaction of the acid group with sulphonyl chloπde to produce the corresponding acid cnioπde The final step in the synthesis of the amido phthalocyanines is the reaction of the acid chloπde with the relevant amine ΞP0519395 descπDes a πumoer of these suostituted amido phthalocyanines wnerem the amido substitution has a maximum of n=2 at toe same time it dεscπbes the production of these derivatives from the prior art method and their use as phthalocyanine dyes and their effect in optical recording elements. It has now been found that substituted amido phthalocyanine derivatives may be readily prepared from phthalocyanine carboxamide by reaction with amine/acid salts. This novel process involves less reaction steps than the prior art process and provides substituted amido phthalocyanine derivatives in high yield. SUMMARY OF THE INVENTION. The present invention relates to a process for the preparation of substituted amido phthalocyanines having the general formula I MPc-(CONR 1 R 2 ) n via the reaction of a phthalocyanine carboxamide having the formula MPc (CONH 2 ) x wherein Pc is a Phthalocyanine ring : M is a hydrogen or a metal capable of forming a metal phthalocyanine and x is a number from 0.1 to 4.0, preferably 1.0 to 3.0, with an amine acid salt denoted by formula II. NH.Z II wherein R 1 and R 2 are independently selected from the group consisting of hydrogen ; an alkyl group having 1-20 carbons ; a cyclic alkyl group ; an aryl group ; an arylalkyl having 1- 20 carbons ; an alcohol group having 2-20 carbons ; an alkyl ammo alkyl group; an aliphatic amine having 1-20 carbons ; an aliphatic amine acid salt having 1-20 carbons ; polyoxyalkylene groups ranging in molecular weight 89-2000 ; polyoxyalkyleneamines ranging in molecular weight 148-4000 ; Z is the hydrogen sulphate or the hydrochloride salt of the amine. It is an object of the present invention to provide a novel process for the synthesis of compounds denoted by formula I which is less labour intensive than the multi stepped oπor art process, and which readily yields products at high effeαency and puπty using a relatively simple method of preparation and isolation The scope of this novel process with regard to reactants and conditions is descπbed herein It is a further object of the present invention to provide novel substituted amido phthalocyanine deπvatives DESCRIPTION The process according to the present invention compπses the reaction of a phthalocyanine carboxamide with an amme/acid salt to provide a substituted amido phthalocyanine The phthalocyanine carboxamide mateπais suitable for use in the present process have the general formula MPc (CONH 2 ) x wherein is a hydrogen or a metal capable of forming a metal phthalocyanine and x is a number from 0 1 to 4 0 Highly preferred for use in the process of the present invention is the carboxamide of copper phthalocyanine wherein x is 1 0 - 3 0 The amine acid salt mateπais suitable for use in the present process have the general formula II NH Z R 2 wherein R 1 and R 2 are independently selected from the group consisting of hydrogen an alkyl group having 1-20 carbons , a cyclic alkyl group , an aryl group , an arylalkyl having 1- 20 carbons , an alcohol group having 2-20 carbons an alkyl ammo alkyl group, an aliphatic amine having 1-20 carbons an aliphatic amine acid salt having 1-20 carbons , polyoxyalkylene groups ranging in molecular weight 89-2000 , polyoxyalkyleneamines ranging in molecular weight 148-4000 Z is the hyαrogen sulphate or the hydrochloπde salt of the amine Examples of Ci - C 20 alkyl groups suitable for use herein include: methyl, propyl, butyl, hexyl, heptyl, dodecyi, hexcadecyl, octadecyl, tert-butyl, oleyl. Preferred alkyl groups F are when R 1 = Hydrogen and R 2 is dodecyi, octadecyl, hexadecyl and oleyl. Examples of C 5 - d 2 cyclo alkyl groups suitable for use herein include: cyclopentyl, cyclohexyl and cyclo-octyl, cyclohexyl being preferred when R 1 = Hydrogen. Examples of C 7 - C 12 Aralkyl groups suitable for use herein include: benzyl or naphthylmethyl, benzyl being preferred when R 1 = Hydrogen. Examples of C 6 - C 1 0 Aryl groups suitable for use herein include : phenyl or napthyl , with a preference for phenyl when R 1 = Hydrogen. The cyclic substituents R 1 ,R 2 namely the cylo-alkyl, aralkyl and aryl substituents may contain one or more substitύent groups. Examples of suitable substituents include Ci - C 8 alkyl groups, such as methyl, ethyl, n-propyl, n-butyl and π-hexyl; Ci - Cβ alkoxy groups such as methoxy, ethoxy, n-propoxy, n-butoxy and n-hexoxy groups; hydroxy groups; nitro groups; and halogeno groups such as chloro, bromo and iodo groups. Examples of C - C 6 alkyl amino alkyl groups suitable for use herein include: dimethylaminoethyl , dimethylaminopropyl , diethylaminopropylamine , dimethylaminopropyl being preffered when R 1 = Hydrogen. Examples of C 2 - C 20 aliphatic amine groups suitable for use herein include: amino ethyl, amino propyl, amino butyl, amino pentyl, amino hexyl, amino heptyl, amino dodecyi amino- octyl. Preferred aliphatic amines are amino hexyl, amino heptyl, amino dodecyi and amino- octyl when R 1 = hydrogen. Examples of the aliphatic amine acid salt groups suitable for use herein are as specified above however as the hydrochloride or the hydrogen sulphate.The preferred amine salts being the hydrochloride amino heptyl, ammo dodecyi and amino-octyl when R 1 = Hydrogen. Examples of C 2 to C 20 alcohol groups suitable for use herein include : 2-hydroxyethyl. 2- hydroxy-i .1 σimethyiethyl. 3 hyαroxy-2.2-dimethyl propyl, 1 hyαroxy hexyl. 1 hyαxoxy propyl. 1 hydroxy pentyl Preferred groups being 2 hydroxy propyl, 1 hydroxy hexyl and 1 hydroxy pentyl when R 1 = Hydrogen . Polyoxyalkylene groups suitable for use herein have the general structure — CHCH2-(OCHCH2)n-R wherein R= methyl and R " can be hydrogen or methyl depending on whether ethylene oxide or propylene oxide has been used in the polymeπsation reaction Suitable polyoxyalkylene groups include polyoxyalkylene amines having the general structure CH 2 CH 2 OCH 2 CH 2 OCH 2 CH r NH 2 These mateπais , known as the Jeffamme Seπes of compounds are available from the Texaco Chemical Company under the trade names Jeffamme M89 (RTM) - Jeffamme M2070(RTM) defining mono amines and Jeffamme EDR 148 (RTM) - Jeffamme D400 (RTM) defining diamines Highly preferred for use as the amine acid salts in the process according to the present invention are the hydrochloπde salts of the amines as hereinbefore detailed The phthalocyanine carboxamide can be reacted with amine salt at from an equimolar amount up to about a 100 fold excess moles , preferably 5 - 20 fold moles of amine salt to 1 mole of phthalocyanine carboxamide The reaction can be earned out in the temperature range 140°C - 320°C, preferably 230 - 300°C The progress of the reaction within this temperature range is rapid, however to ensure completion the reaction mixture should be heated for 0 5 - 20 hours, preferably 1 - 3 hours The use of high boiling organic solvents may be employed such as nitrobenzene, naphthalene ortho-nitro toluene and mixtures thereof The preferred method is to use the melt of the amine acid salt as the solvent TIIS can be done due to τ he very high boiling points of the amine acid salts typically in excess of 250°C, hence a melt reaction can be carried out practically and successfully within this temperature range. In most cases the isolation of the products is accomplished by separation and filtration means, as an extensive range of the amine acid salts used according to the process of the present invention are soluble in hot water. In most cases after the reaction is complete the excess amine acid salt can be removed by rinsing with hot water, before and during filtration. The use of other (water insoluble) amine acid salts requires rinsing with chloroform and ethanol to remove the excess amine salt, before filtration is carried out. Where the amine acid salts are not available in commercial form they may be readily made from the parent amine and the appropriate acid. The present invention additionally provides novel amido substituted phthalocyanine derivatives having the general formula I: MPc-(CONR 1 R 2 ) n I wherein Pc is a Phthalocyanine ring; M is a hydrogen or a metal capable of forming a metal phthalocyanine and x is a number from 0.1 to 4.0, preferably 1.0 to 3.0; and R 1 and R 2 are indepentely selected from hydrogen ; polyoxyalkylene groups ranging in molecular weight 89-2000 ; polyoxyalkyleneamines ranging in molecular weight 148-4000. The following non-limiting examples further illustrate the process and products according to the present invention. Reactions of the carboxamide of phthalocyanine and the amine acid salt go fully to completion unless specifically stat4ed to the contrary. However the final product shows quantities of Phthalocyanine present which originates from the reaction of the trimeilitic acid (anhydride) and phthaiic acid (anhydride) in the production of the carboxamide. For completeness a description of the production of mono carooxamide copper phthalocyanine CuPc(CONH 2 ) 1 and tetra carboxamide copper phthalocyanine CuPc ( CONH 2 ) 4 are included. Preparation of CuPc(CONH ? ) A mixture of 13g cupric chloride , 65 g of phthaiic acid, 27 g of trimellitic acid and 0.4g of ammonium molybdate were heated in the presence of 243g of urea at about 180°C for a period of 15 hours. The reaction mixture was then allowed to cool and dissloved in 98% H2SO4 at 60°C with stirring , then drowned out into an ice-bath containing 500g of ice and 3 litres of cold water, ensuring that the temperature < 5°C .Filtration and washing is then carried out to yield 53g of approx 88% pure CuPc(CONH 2 )ι as measured by sulphuric acid and eerie sulphate assay. Preparation of CuPc(CQNH?)a A mixture of 13g cupric chloride , 122 g of trimellitic anhydride and 0.4g of ammonium molybdate were heated in the presence of 243g of urea at about 180 °C for a period of 15 hours. The reaction mixture was then allowed to cool and dissloved in 98% H2SO4 at 60°C with stirring ,then drowned out into an ice-bath containing 500g of ice and 3 litres of cold water , ensuring that the temperature < 5°C .Filtration and washing is then carried out to yield 77g of approx 88% pure CuPc(CONH 2 ) 4 . as measured by sulphuric acid and eerie sulphate assay. In the following examples, the Fourier - Transform Infra - Red Spectra of both the starting material, namely CuPc (CONH 2 ) χ and each of the compounds of formula 1 according to the invention are recorded on a Philips PU9800 FTIR Spectrophotometer, as KBr discs between 4000 and 400cm "1 . The spectra is used in conjunction with MALDI-TOF mass-spectra of the compounds of formula I to characterise both the reaction efficiency, and the reaction products. EXAMPLE 1 Preparation of mono propylamido copper phthalocyanine. 5g of copper phthalocyanine mono carboxamide (88% Pure) and 10g of propyiamine hydrochloride were mixed well manually and heated to about 280°C for about 1 hour using an iso-mantle. The reaction mixture was allowed to cool to about 60°C and then reslurried by addition of water at about 80 °C , filtration of the slurry and further washing with about 80 °C water was carried out to remove excess amine hydrochloride. The filtered .washed product was dried at about 70°C in an oven to give 4.52g of mono propylamido copper phthalocyanine. The FTIR spectrum of the CuPc carboxamide starting material and that of the final product are clearly different. Very strong peaks appear at 2900cm "1 and 2850cm "1 in the propylamido CuPc but not in that of the CuPc monocarboxamide. This is strong evidence for, and very characteristic of alkyl stretching activity which can be associated with the propyl group. EXAMPLE 2 Preparation of dodecylamido copper phthalocyanine. 19.4g of dodecylamine was placed in a round bottom flask and Hydrochloride gas bubbled continuously through the amine for about 1 hour with gentle heat about 50°C to form dodecylamine hydrochloride. 5g of CuPc monocarboxamide was then added all together and thoroughly mixed together manually. The mixture was heated to about 280°C for about 2 hours. The reaction mixture was allowed to cool to room temperature then reslurried in a minimum quantity of chloroform, and added slowly portionwise to approx 400mls of ethanol with stirring using a magnetic stirrer. Filtration and washing with ethanol was carried out and the resultant product dried at 70 °C in an oven to give 4.69g mono dodecylamido CuPc. The FITR Spectrum of the CuPc carboxamide and the final product are cleariy different. Very strong peaks appear at 2900cm "1 and 2850cm '1 in the dodecylamido CuPc but not in that of the CuPc monocarboxamide. This is strong evidence for, and very characteristic of alkyl stretching activity which can be associated with the dodecyi group. MALDI-TOF mass spectra of the CuPc carboxamide and the final product are also cleariy different. In the final product the mass spectra cleariy shows the presence of mono dodecyi amiαo CuPc by an intense peak at 790m/z. The starting material has no corresponding peaks at these mass to charge ratios. EXAMPLE 3 Preparation of octadeeylamido copper phthalocyanine. 5g of copper phthalocyanine mono carboxamide 88% Pure and 32g of octacdecylamine hydrochloride are mixed well manually and heated to about 280°C for about 2 hours using an isomantle. The reaction mixture was allowed to cool to room temperature and the product isolated as for Example 2, to give 4.91 g mono octadeeylamido CuPc. FTIR spectra of starting material and final product were clearly different with very strong peaks at 2900cm "1 and 2850cm "1 for the final product, but not in the case of the CuPc carboxamide. This is strong evidence, and characteristic of alkyl stretching activity associated with the octadecyl group. Maldi-toff mass spectra of the final product highlights an intense peak at 874 m/z which represents mono octadeeylamido CuPc. The starting material has no corresponding peaks at this mass to charge (m/z) ratio. EXAMPLE 4 Preparation of tetra propylamido copper phthalocyanine. 3.5g of tetra carboxamide copper phthalocyanine was mixed with 18g of propylamine hydrochloride manually and heated to about 180 °C using an oil bath for about 20 hours. The reaction mixture was then allowed to cool to room temperatureand reslurried with hot water at about 80°C, followed by filtration and washing with hot water at about 80°C.T e resulting filtercake was given a final acetone wash, and dried at about 70 °C in an oven to give 3 g tetrapropylamido CuPc. FTIR spectra clearly highlights the alkyl strech of the propyl group for tetra propylamido CuPc at 2900cm-1and 2850cm-1.The maldi mass spectra also highlights the statistical isomeric mix of tetra substituted product eg. 794m/z represents the mono isomer, 839m/z represents the di isomer, 883m/z represents the tri isomer and 925m/z represents tetra isom , EXAMPLE 5 Preparation of mono benzylamido copper phthalocyanine 2.0 g of mono carboxamide copper phthalocyanine was mixed manually with 5.42 g of aniline hydrocnioπde manually in a test - tuoe and heated to about 300 " C "'or about 30 minutes using a bunsen burner. The reaction mixture was allowed to cool to room temperature and reslurried in hot water at about 80°C to disslove excess aniline hydrochloride. Filtration and washing was carried out with hot water at about 80°C, followed by a final ethanol wash. The resultant filtercake was dried at about 70 °C in an oven to give 1.98 g of mono benzylamido CuPc. Maldi mass spectra of the resultant product clearly shows the presence of an intense peak at 695m/z which corresponds to mono benzylamido CuPc , this peak is not present in the starting material. EXAMPLE 6 Preparation of mono phenaethylamido copper phthalocyanine 2.0 g of mono carboxamide copper phthalocyanine was mixed with 6.62 g of phenaethylamine hydrochloride manually in a test - tube and heated to about 300 °C for about 30 minutes using a bunsen burner. The reaction mixture wasallowed to cool to room temperature and reslurried in hot water at about 80°C to disslove excess phenaethylamine hydrochloride. Filtration and washing was carried out with hot water at about 80°C followed by a final ethanol wash. The resultant filtercake was dried at about 70 °C in an oven to give 2.2 g of mono phenaethylamido CuPc. The FTIR spectrum of the product indicates infra red activity of a secondary amide at 1640cm- 1 compared to the primary amide of the starting material which has activity at 1605cm-1.However more conclusively Maldi mass spectra of the product clearly shows an intense peak at 724.2 m/z which corresponds to mono phenaethylamido CuPc , this peak is not present in the starting material.

Claims: CLAIMS 1. A process for the preparation of substituted amido phthalocyanines having the general formula I: MPc-(CONR 1 R 2 ) n I via the reaction of a phthalocyanine carboxamide having the formula MPc (CONH 2 ) x wherein Pc is a Phthalocyanine ring ; M is a hydrogen or a metal capable of forming a metal phthalocyanine such as Mg, Al, Ni, Fe, Zn, Pb, Sn or Cu and x is a number from 0.1 to 4.0, with an amine acid salt denoted by formula II: R 1 ^^ NH.Z II 2 --— wherein R 1 and R 2 are independently selected from the group consisting of hydrogen ; an alkyl group having 1-20 carbons ; a cyclic alkyl group ; an aryl group ; an arylalkyl having 1-20 carbons ; an alcohol group having 2-20 carbons ; an alkyl amino alkyl group; an aliphatic amine having 1-20 carbons ; an aliphatic amine acid salt having 1-20 carbons ; polyoxyalkylene groups ranging in molecular weight 89-2000 ; polyoxyalkyleneamines ranging in molecular weight 148-4000 ; Z is the hydrogen sulphate or the hydrochloride salt of the amine. 2. A process according to Claim 1 wherein the phthalocyanine carboxamide, MPc (CONH 2 ) x , has the following substituents: Pc is a Phthalocyanine ring ; M is Cu and x is a number from 1.0 to 3.0. 3. A process according to Claim 1 or 2 wherein the C-, - C 20 alkyl groups of the amine acid salt are selected from methyl, propyl, butyl, hexyl, heptyl, dodecyi, hexcadecyl, octadecyl, tert-butyl, oleyl and mixtures thereof. 4. A process according to any of Claims 1 to 3 wherein the wherein the R 1 and R 2 groups of the amine acid salt are: R 1 = hydrogen and R 2 is an dodecyi, octadecyl, hexadecyl or oleyl alkyi group. 5. A process according to any of Claims 1 to 4 wherein the cycio alkyl groups of the amine acid salt are selected from C 5 - C 12 cyclo alkyl groups such as cyclopentyl, cyclohexyl and cyclo-octyl wherein cyclohexyl is preferred when R 1 is hydrogen. 6. A process according to any of Claims 1 to 5 wherein the aralkyl groups of the amine acid salt are C 7 - Cι 2 aralkyl groups selected from benzyl or naphthylmethyl and wherein benzyl is preferred when R 1 is hydrogen. 7. A process according to any of Claims 1 to 6 wherein the alcohol groups of the amine acid salt are selected from C 2 to C 20 alcohol groups such as 2-hydroxyethyl, 2-hydroxy- 1,1 dimethylethyl, 3 hydroxy-2,2-dimethyl propyl, 1 hydroxy hexyl, 1 hydroxy propyl, 1 hydroxy pentyl , preferably 2 hydroxy propyl, 1 hydroxy hexyl and 1 hydroxy pentyl are used when R 1 is hydrogen . 8. A process according to any of Claims 1 to 7 wherein the aryl groups of the amine acid salt are C 6 - Cι 0 aryl groups selected from phenyl or napthyl, with a preference for phenyl when R 1 is hydrogen. 9. A process according to any of Claims 1 to 8 wherein the amino alkyl groups of the amine acid salt are C 4 - C 6 alkyl amino alkyl groups selected from dimethylaminoethyl , dimethylaminopropyl , diethylaminopropylamine and wherein dimethylaminopropyl is prefered when R 1 is hydrogen. 10. A process according to any of Claims 1 to 9 wherein the aliphatic amine groups of the amine acid salt are C 2 - C 2 n aliphatic amine groups selected from amino ethyl, amino propyl, amino butyl, amino pentyl, amino hexyl, amino heptyl, amino dodecyi amino-octyl and are prefereably selected from amino hexyl, amino heptyl, amino dodecyi and amino- octyl when R 1 is hydrogen. 11. A process according to any of Claims 1 to 10 wherein the polyoxyalkylene groups of the amine acid salt are selected from materials having the general structure: -CHCH2-(OCHCH2)n-R h- wherein R= methyl and R ' can be hydrogen or methyl depending on whether ethylene oxide or propylene oxide has been used in the polymerisation reaction. 12. A process according to any of Claims 1 to 11 wherein the polyoxyalkylene amine groups of the amine acid salt are selected from materials having the general structure: CH 2 CH 2 OCH 2 CH 2 OCH 2 CH NH 2 13. A process according to any of Claims 1 to 12 wherein the amine acid salt is a hydrochloride. 14. A process according to any of Claims 1 to 13 wherein the level of amine salt to phthalocyanine carboxamide is in the molar ratio of from about 1:1 to about 100:1, preferably from about 5:1 to about 20:1 moles of amine salt to phthalocyanine carboxamide. 15. A process according to any of Claims 1 to 14 wherein the temperature of the melt reaction between the amine acid salt and the phthalocyanine carboxamide is from about 140°C to about 320°C, preferably from about 230°C to about 300°C. 16. A process according to any of Claims 1 to 15 wherein the melt reaction mixture is heated for from about 0.5 to about 20 hours, preferably from about 1 to about 3 hours. 17. A process according to any of Claims 1 to 16 substantially as described in Examples 1 to 6. 18. Substituted amido phthalocyanines obtainable by the process according to any of Claims 1 to 17 and having the general formula I: MPc-(CONR 1 R 2 ) n I wherein Pc is a Phthalocyanine ring; M is a hydrogen or a metal capable of forming a metal phthalocyanine and x is a number from 0.1 to 4.0, preferably 1.0 to 3.0; and R 1 and R 2 are indepentely selected from hydrogen ; polyoxyalkylene groups ranging in molecular weight 89-2000 ; polyoxyalkyleneamines ranging in molecular weight 148- 4000.

Inventors: EWINS CAIRAN THOMAS, HEALY THOMAS, EWINS, CAIRAN, THOMAS, HEALY, THOMAS
Applicants: CIBA SC HOLDING AG, CIBA SPECIALTY CHEMICALS HOLDING INC.
Application year: 1999
Main classification: C09B47
IPC codes: C07D487, C09B47