Title of Invention

NEW BISAZO PIGMENTS FROM HOMOPHTHALIMIDE DERIVATIVES

Abstract

The present invention encompasses new bisazo pigments of formula I, prepared by tetrazotising different aromatic diamines like :( ex. 4,4'-diaminobenzanilide, 4,4'- diaminosulfanilide, 4,4'-diaminoazobenzene, 3',3'-di-n-propoxybenzidine, 3,3'-di-n- l! butoxybenzidine etc.) and coupling with Homophthalimides. Where, X = part of an aromatic diamine, R = H, C1-6 alkyl,C6-10 aryl, C7-.10 aralkyl, -CH2CH2OH, -CH2CH2CN etc.

Full Text

FORM 2 THE PATENTS ACT, 1970 (39 OF 1970) & THE PATENTS RULES, 2003 COMPLETE SPECIFICATION ( Section 10 and rule 13 ) 1. "NEW BISAZO PIGMENTS FROM HOMOPHTHALIMIDE DERIVATIVES" 2. (a) Kanetkar Vinod Rajaram (b) Dyestuff Technology Division, Institute of Chemical Technology, University of Mumbai, Nathalal Parekh Marg., Matunga. Mumbai 400019, Maharashtra, India, (c) INDIAN. The following specification particularly describes the invention and the manner in which it is to be performed. The present invention encompasses new Bisazojlpigments from Homophthalimide of formula I, prepared by tetrazotising different aromatic diamines like ( ex. 4,4'-diaminobenzanilide, 4,4'-diaminosulfanilide, 4,4'-diaminoazobenzene, 3,3'-di-n-propoxybenzidine, 3,3'-di-n-butoxybenzidine etc.) and coupling with Homophthalimide. Where, X = part of an aromatic diamine, R = H, C1-6 alkyl, C6-10 aryl, C7-10 aralkyl, -CH2CH2OH, -CH2CH2CN etc. Field of invention; The present invention relates to new Bisazo pigments from Homophthalimide of formula I prepared by tetrazotising diamines and coupling with two moles of Homophthalimide derivatives. Where, X = part of an aromatic diamine, R = H, C1-6 alkyl, C6-10 aryl, C7-10 aralkyl, -CH2CH2OH, -CH2CH2CN etc. More specifically this invention relates to the use of Homophthalimide and different nonmutagenic and less toxic diamines for the preparation of pigments. Background of Invention: This invention relates to preparation of new Bisazo pigments from Homophthalimides. Bisazo pigments were prepared by tetrazotisation of different aromatic amines and coupling with Homophthalimide derivatives. Use of Homophthalimide as a coupling component is described in the Germen li Patent No.2,215,497. In this azo pigments for printing inks were prepared by diazotizing different aromatic amines and coupling with Homophthalimide and several lake pigments were also prepared. Present invention encompasses bisazo pigments from Homophthalimide having good fastness properties. Germen Patent Ger. Offen. 2,555,910 describes greenish yellow to reddish yellow disperse dyes prepared by using Homophthalimide as a coupling component. These dyes are fast to light and thermal fixation. Present invention encompasses bisazo pigments from Homophthalimide having good fastness properties. Homophthalimide was used as a coupling component by Tilak et.al. as described in an Indian Patent No. 154460., in which yellow to violet azo N-substituted Homophthalimide disperse dyes were prepared for application to synthetic fibers. Several aromatic amines were diazotized and coupled with N-substituted Homophthalimide in an aqeous alkaline solution and precipitated dyestuff was separated. Present invention encompasses bisazo pigments from Homophthalimide having good fastness properties. Indian Patent No. 148462 discloses a process for the preparation of yellow to scarlet azo cationic dyes suitable for application to polyacrylonitrile fibers. In this patent p-amino-phenacylammonium chloride was diazotized and coupled with different couplers e.g. N,N-dimethylaniline, β-naphthol, etc., then the resulting dye was quaternised with aqueous trimethylamine at 25-45° C to give the azo cationic dyes. Present invention encompasses bisazo pigments from Homophthalimide having good fastness properties. Japanese patent No. Jpn.Kokai Tokkyo Koho JP 07,168,379 discloses colorants prepared by tetrazotising 4,4'-diaminobenzanilide and coupling with naphthol AS to give electrographic photoreceptors. Present invention encompasses Homophthalimide derivatives as couplers to give bisazo pigments having good fastness properties. Germen patent No. Ger offen. 2,651,919 discloses disazo pigments prepared from 4,4'-diaminobenzanilide, it was tetrazotised and coupled with 5-(acetoacetylamino)benzimidazolone to give bisazo pigment. Present invention encompasses Homophthalimide derivatives as couplers to give bisazo pigments having good fastness properties. Two Japanese patents JP 59,33,456 and JP 58,217,556 discloses colorants prepared from 4,4'-diaminoazobenzene as a tetrazo, component and various couplers used are naphthol AS, pyrazolones, and naphthalimides etc. Present invention encompasses Homophthalimide derivatives as couplers to give bisazo pigments having good fastness properties. European patent No. EP 78,575 discloses colorants from substituted 4,4'-diaminoazobenzene and naphthol AS. These colorants are used as an electrophotographic photosensitive material. Present invention encompasses Homophthalimide derivatives as couplers to give bisazo pigments having good fastness properties. European patent No. EP 94 079 discloses Photosensitive materials for electrophotography prepare by tetrazotising 4,4'-diaminoazoenzene and coupling with couplers like naphthol AS, pyrazolones, acetoacetanalides, naphthalimides etc. Present invention encompasses Homophthalimide derivatives as couplers to give bisazo pigments having good fastness properties. Japanese patent no. Jpn.Kokai.Tokkyo Koho JP 01,234,470 discloses disazo pigments from 4,4'-diaminobenzanilide, and 4,4'-diaminoazobenzene. Pyrazolone type couplers are used in this patent. Present invention encompasses Homophthalimide derivatives as couplers to give bisazo pigments haying good fastness properties. Delia Porta G et.al reported in Cancer Letters 14(3), 1981 , 329-336, that 4,4'-diaminoazobenzene and 4,4'-diaminobenzanilide are noncarcinogenic in nature. Thus there is no report in the prior art of use of Homophthalimide to prepare bisazo pigments. The present invention disclose use of Homophthalimide derivatives to prepare novel bisazo pigments having excellent fastness properties and application in paints, printing inks and polymers. Nonmutagenic and less toxic diamines were used for the synthesis of these pigments. Further such high molecular size of pigments will impart good fastness properties. Objectives of the Invention: It is therefore objective of the present invention to synthesize novel Bisazo pigments from Homophthalimide derivatives having good fastness properties. Another object is to exploit Homophthalimide for the synthesis of Bisazo pigments. A further object is to provide new class of pigments that will display excellent overall stability and fastness characteristics. Yet further object is to use less toxic and nonmutagenic diamines to synthesize bisazo pigments and to prepare high molecular weight and large molecular size pigments from Homophthalimide. These and still other objects, which will appear even more clearly to the skilled in the art, are achieved according to this invention. Summary of the Invention; The present invention encompasses new Bisazo pigments from Homophthalimide of formula I prepared by tetrazotising different aromatic diamines (ex. 4,4'-diaminobenzanilide, 4,4'-diaminosulfanilide, 4,4'-diaminoazobenzene, 3,3'-di- n-propoxybenzidine) and coupling with Homophthalimide. (I) Where, X = part of an aromatic diamine, R = H, C1-6 alkyl, C6-10 aryl, C7-.10 aralkyl, -CH2CH2OH, -CH2CH2CN etc. The new pigments corresponding to formal I allow one to obtain paints, printing inks and coloration of polymers of shades ranging from yellow to red and good overall characteristics in particular solvent light and fastness. Detailed Description of the Invention; Where, X = part of an aromatic diamine such as As described earlier, the invention concerns a new Bisazo pigments from Homopthalimide having the general formula I CH3CH2CH2CH20 R = H, C1-6 alkyl, C6-10 aryl, C7.10 aralkyl, -CH2CH2OH, -CH2CH2CN, NHCOR' Where R' = C6H5, 4-MeC6H4, p-N02C6H4 These pigments are also useful for preparing paints, printing inks and for coloration of polymers. The pigments of general formula I are obtained by tetrazotising aromatic diamines and coupling with Homophthalimide derivatives. Different aromatic diamines used are 4,4'-diaminobenzanilide, 4,4'-diaminosulfanilide, 4,4'-diaminoazobenzene, 3,3'-di-n-propoxybenzidine, 3,3'-di-n-butoxybenzidine , 4,4'-diaminodiphenylsulfone, 4,4'- diaminodiphenylamine, Bis(4-aminophenyl)methanone, 3,3'-di-n-propylbenzidine, 3,3'-di-( P-methoxyethoxy) benzidine, 2,2'-dimethoxy-5,5'-dipropoxybenzidine, 2,2'-dichloro-5,5 '-dipropoxybenzidine etc. The reaction is as shown in Scheme 1 Scheme I. Typically respective diamine is dispersed in an ice/water mixture in the presence of HCI. The mixture was stirred at 5°C, and sodium nitrite solution was added at such a rate to maintain a slight excess of HNO2. The tetrazotisation was continued for 30 min and the resulting tetrazonium salt was added drop wise at 5°C, to the coupling component dispersion, obtained by dissolution in a H2O/ NapH mixture, followed by precipitation with CH3COOH at pH 7, at such a rate that no presence of tetrazo intermediate was observed. The coupling was continued for several hours, and after the reaction was completed, the reaction mixture was heated to boiling. The obtained pigment was filtered hot, washed with hot water and dried. Different Homophthalimide derivatives which can be used are OH Homophthalimide derivatives Where, R = H, C1-6 alkyl, C6-10 aryl, C7-.10 aralkyl, -CH2CH2OH, -CH2CH2CN, NHCOR' Where R' = C6H5, 4-MeC6H4, p-N02C6H4 The ratio of diamine to Homophthalimide ranges from 1:2 to 1:2.2. Diazotization as well as coupling reactions are carried out in a temperature range between 0-10° C. Completion of reaction takes around 7-10 hrs. Following are some bisazo pigments of the invention. A Bisazo pigment 4-(( 1,3-dioxo-1,2,3,4-tetrahydroisoquinolin-4yl)diazenyl)-N-(4-(( 1,3-dioxo-1,2,3,4- tetrahydroisoquinolin-4-yl)diazenyl)phenyl)benzamide of structure A Bisazo Pigment 4-((l,3-dioxo-l,2,3,4-tetrahydroisoquinolin-4yl)diazenyl)-N-(4-((l,3-dioxo-l,2,3,4- tetrahydroisoquinolin-4-yl)diazenyl)phenyl)benzenesulfonamide of structure A Bisazo pigment 4,4 '-(4,4'-(diazene-l,2-diyl)bis(4, l-phenylene))bis(diazene-2,l -diyl)diisoquinoline-1,3(2 H , 4 H)-dione of structure A bisazo pigment 4,4'(33'-dipropoxybiphenyl-4,4,-diyl)bis(diazene-2,J-diyl)diisoquinoline-l,3(2 H,4 H)-dione of structure A bisazo pigment 4,4'-(3,3'-dibutoxybiphenyl-4,4'-diyl)bis(diazen;e-2,J-diyl)dusoquinoline-l,3(2 H,4 H)-dione of structure The following examples further describe and demonstrate embodiments within the scope of the present invention. The examples are given solely for the purpose of illustration and not to be constructed as limitations of the present invention, as many variations are possible without departing from the spirit and scope of the invention. Example 1: A suspension of 4,4'- diaminobenzanilide 5.69g ( 0.025 mole) in H20 ( 30 g ), HC1 30% ( 13 ml) and ice ( 10 g ) was prepared and stirred for several minutes, to this reaction mixture at 0-5°C temperature, NaN02 3.45 g ( 0,05 mole ) dissolved in H20 ( 8.2 g ) was added dropwise at a such a rate so as to maintain a slight excess of HNO2. The tetrazotisation salt solution was then added ; dropwise at 5°C, at pH 7 to Homophthalimide 8 g ( 0.05 mole ) obtained by its dissolution in H20 (120 g) containing NaOH ( lg ), followed by precipitation with acetic acid ( 2 ml), at a such a rate that no presence of tetrazointermediate was observed. The coupling reaction was continued for several hours and next the reaction mixture was'heated to the boil. The pigment was filtered hot, boiled several times with hot water, filtered again and dried at 40°C. A product yield of 84% was obtained. The elemental analysis is as shown below. Found percentage C = 65.4, H = 3.8, N = 17.4, O = 14.2 Theoretical percentage for C31H21N7O5, C = 65.1, H = 3.6, N = 17.6, O - 14.0 The product showed maximum absorption in the visible spectrum at 449 nm (DMF) Example 2 : The charge similar to that given in Example lwas used except that 6.57 g of 4,4'-diaminosulfanilide was used instead of 4,4'-diaminobenzanilide. A product yield of 70% was obtained. The elemental analysis is as shown below. Found percentage C = 59.2, H = 3.5, N = 16.7, 0 = 15.5, S = 5.5 Theorotical percentage for C30H21N7O6S, C = 59.3, J H = 3.4, N = 16.4, O = 15.8 The product showed maximum absorption in the visible spectrum at 419 nm (DMF) Example 3 : The charge similar to that given in Example 1 was used except that 5.3 g of 4,4'- diaminoazobenzene was used instead of 4,4'-diaminobenzanilide. A product yield of 80% was obtained. The elemental analysis is as shown below. Found percentage C = 64.5, H = 3.7, N = 20.2, 0 = 11.7 Theorotical percentage for C3oH2oN804, C = 64.7, H = 3.5, N = 20.1,0=11.5 The product showed maximum absorption in the visible spectrum at 500 nm ( DMF) Example 4 : The charge similar to that given in Example 1 was used except that 7.5 g of 3,3'-di-n- propoxybenzidine was used instead of 4,4'-diaminpbenzanilide. A product yield of 86 % was obtained. The elemental analysis is as shown below. Found percentage C = 67.3, H = 4.7, N = 13.2, O = 15.0 Theorotical percentage for C36H32N606, C = 67.08, H = 4.9, N = 13.0, O = 14.9 The product showed maximum absorption in the visible spectrum at 487 nm (DMF) Example 5 : The charge similar to that given in Example 1 was used except that 7.5 g of 3,3'-di-n- butoxybenzidine was used instead of 4,4'-diaminobenzanilide. A product yield of 80 % was obtained. The elemental analysis is as shown below. Found percentage C = 67.75, H = 5.32, N = 12.57,, O = 14.22 Theorotical percentage for C38H36N606, C = 67.85 H = 5.35, N = 12.5, O = 14.28 The product showed maximum absorption in the visible spectrum at 487 nm ( DMF) Example 6: The charge similar to that given in Example 1 was used except that 8.75 g of N-methyl Homophthalimide was used instead of Homophthalimide . A product yield of 84% was obtained. The elemental analysis is as shown below. Found percentage C = 66.22, H = 4.19, N = 16.32, O = 13.81 Theorotical percentage for C33H25N705, C = 66.11, H = 4.17, N = 16.36, O = 13.35 The product showed maximum absorption in the visible spectrum at 448 nm ( DMF) . Example 7 : The charge similar to that given in Example 1 was used except that 9.45 g of N-ethyl Homophthalimide was used instead of Homophthalimide . A product yield of 90% was obtained. The elemental analysis is as shown below. Found percentage C = 66.91, H = 4.68, N = 16.391] O = 12.71 Theorotical percentage for C35H29N7O5, C = 66.98!', H = 4.62, N = 15.33, O = 12.75 The product showed maximum absorption in the visible spectrum at 449 nm (DMF) Example 8 : The charge similar to that given in Example 1 was used except that 10.15 g of N-propyl Homophthalimide was used instead of Homophthalimide . A product yield of 83% was obtained. The elemental analysis is as shown below. ' Found percentage C = 66.71, H = 5.35, N = 14.11', O = 12.58 Theorotical percentage for C37H33N7O5, C = 67.78, H = 5.03, N = 14.96, O = 12.21 The product showed maximum absorption in the visible spectrum at 447 nm (DMF) Example 9 : The charge similar to that given in Example 1 was used except that 11.85 g of N-phenyl Homophthalimide was used instead of Homophthalimide . A product yield of 81% was obtained. The elemental analysis is as shown below. Found percentage C = 71.39, H = 3.25, N = 13.82' 0= 11.81 Theorotical percentage for C43H29N7O5, C = 71.36, H = 3.99, N = 13.55, O = 11.06 The product showed maximum absorption in the visible spectrum at 450 nm (DMF) It will be understood that various details of the present invention may be changed without departing from the spirit and scope of invention. Furthermore the foregoing examples are for illustrative purpose only, and in no way are indented to limit the scope of the invention as defined by the claims. I claim; 1) Bisazo pigments from Homophthalimide of formula I Where, X = part of an aromatic diamine, R = H, C1-6 alkyl, C6-10 aryl, C7-.10 aralkyl, -CH2CH2OH, -CH2CH2CN. 2) A Bisazo pigment as claimed in claim 1 where different aromatic diamines are 4,4'-diaminobenzanilide, 4,4'-diaminosulfanilide,4,4'-diaminoazobenzene,4,4'-diaminodiphenylsulfone,4,4'- diaminodiphenylamine,Bis(4-aminophenyl)methanone, 3,3'-di-n-propoxybenzidine, 3,3'-di-n-butoxybenzidine, 3,3'-di-n-propylbenzidine, 3,3'-di-( (3-methoxyethoxy) benzidine, 2,2'-dimethyl-5,5'-dipropoxybenzidine, 2,2' -dimethoxy-5,5' -dipropoxybenzidine, 2,2'-dichloro-5,5 '-dipropoxybenzidine j 3) A Bisazo pigment as claimed in claim 1 where {different Homophthalimide derivatives are , R = H, CH3,CH2CH3, isopropyl, -CH2CH2CN, -CH2CH2OH, -C6H5. 4) A bisazo pigment as claimed in claim 1 and 3 where R = NHCOR' : Where R' = C6H5, 4-MeC6H4, p-N02C6H4 5) A bisazo pigment as claimed in claim 1 is 4-((l,3-dioxo-1,2,3,4-tetrahydroisoquinolin-4yl)diazenyl)-N-(4-((l,3-dioxo-l,2,3,4-tetrahydroisoquinolin-4-yl)diazenyl)phenyl)benzamide of following formula 6) A bisazo pigment as claimed in claim 1 is 4-((l,3-dioxo-l,2,3,4-tetrahydroisoquinolin-4yl)diazenyl)-.N-(4-(( 1,3-dioxo-1,2,3,4-tetrahydroisoquinolin-4-yl)diazenyl)phenyl)benzenesulfonamide of following formula 7) A bisazo pigment as claimed in claim 1 is 4,4-(4,4'-(diazene-l,2-diyl)bis(4, l-phenylene))bis(:diazene-2,l -diyl)diisoquinoline- l,3(2 H,4 H)-dione of following formula 8) A bisazo pigment as claimed in claim 1 is 4,4'(33'-dipropoxybiphenyl-4,4'-diyl)bis(diazene-2,1-diyl)diis(xiuinoline-l,3(2-H,4 H)-dione of following formula 9) A bisazo pigment as claimed in claim 1 is 4,4'-(3,3'-dibutoxybiphenyl-4,4'-diyl)bis(diazene-2,l-diyl)diisoquinoline-l,3(2-H,4H)-dione of following formula. 10) A bisazomethine pigment as claimed in claims 1 to 9 substantially as herein described with forging description and examples. Date: O2.03.06 Kanetkar Vinod Rajaram

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