Document QMXrjgZp1ovjBQXq2eBxwQDz4

E. I. DU PONT DE NEMOURS 6* COMPANY PIGMENTS DEPARTMENT 256 VANDERPOOL STREET NEWARK, NEW JERSEY Serial No. 8-53-8 Copy No. X Numerical File Period Covered NEWARK PLANT CHEMICAL DIVISION - COLORS JACES08 UB08ATOH? PX0MEHT8 GROUP RESEARCH REPORT l x g h t f as t azo - wmm c impl bx s s mm 1951 to ms x, 1952* l FILE: DATE: fffll >*ll hmm NJ 8747 N41997 Copies to: X. numerical File 2. Chemical Division Office $223r*434- , 3. Library File f321.4l)4. J, S* Tully/A. Siegel/Library 5* W. F. Speageaan/Library 6. M. S.Struve, Jackson Lab. 7. Extra 3* Extra 1 JACKSON LABORAIOHT PIGMENTS GROUP RESEARCH REPORT LIGHTFAST AZO * PIGMENT COMPLEXES JUNE 4, 1951 to MAT 1, 1952. CHARGE: A-II-268 DATE SUBMITTED: 3/20/s DATE ISSUED* 4/21/53 DUP050069283 The unusually good lightfastness of Green-Gold, YT-5G2-l>r (HI complex of parachloraniline coupled to 2,4>-dihydrexy qainolioe) has led to the search for other metallized azo pigments of similar properties# A great number of combinations were prepared and examined by Jackson laboratory but a review of this work did not disclose any products which possessed both the relatively good color value and lightfastaess of YT-562-D. The object of the pre sent investigation was the preparation and evaluation of metal complexes, derived from coupling components which were analogous to 2,4-dihydroxy quinoline in having a /3 diketo structure or the corresponding ensile form* 1 A number of coupling components possessing some of the structural characteristics of 2,4-difaydroxy quinoline were prepared or obtained from other sources and When possible were coupled to common diazo components and converted to their nickel or copper complexes* Hone of the metallic derivatives obtained showed any advantage over Green-Gold, YT-562-D, and many of them were Inferior in respect wither to tinctorial properties or lightfastness* It was not found possible to form metal chelates of azo dyestuffs in which the diazo components were devoid of addle groups and the second components were acyclic compounds such $s acetyl acetone or in which the active methylene group was part of a straight chain as in acatoacetanilide. This was also the ease with the homologous components - benzoyl acetone and benzoyl acet anilide* Similar inability to metallize was observed on the part of the coupled products from 2-acetonyl benzamlnazole and 2-acetonyl benzthiazole. 2-phenacyl benzamlnazole coupled with difficulty and the product metallized slowly and incompletely* In contrast, analogs of 2,4-dihydroxy quinoline* such as 2,4-dlhydroxy-IMaethyl quinoline, 4-hydroxy-2-methyl quinoline, aad benzotetrode acid (the oxygen analog of BBQ) when coupled to dlazotized parachloraniline * gave dyestuffs which combined readily with dekel* Of these only the 0 analog approached YT-562-D in shade and lightfastaess and it was considerably weaker and duller. The other products were browns of poor lightfastaess and bleed resistance* 2-hydroxyA-methyl quinoline could not be coupled under the usual conditions due to the relatively inactive CBg - group* DUP050069284 2 Two isomers of dlhydroxy quinoline - 1,3 and 1,4isoquinolinediol - also gave less satisfactory results than 2,4-DBg* The former, coupled to aniline and parachloraniline. did not react with nichel tut formed a dull yellow copper derivative which was poor in lightfastness and bleed. When coupled to 4-chloranthranllie acid, a copper derivative (a partially completed metal salt) was obtainable, which exhibited excellent llghtfastness in full shade drawdown* However, poor bleed resistance, as well as its brownnose, make it of little value. 1,4--isoquinolinediol coupled to parachlor aniline gave violet nickel and copper derivatives which were too dull in shade and too poor in oil bleed to be of interest* The copper couples; possessed good llghtfastness in full shads drawdown* The greater ease of metallization of many heterocyclic compounds was confirmed by results with 1-phenyl-3-methyl-5-pyrazolone and 5,5-diesthyl cyclohexanedione-1,3. In both cases nickel derivatives could be prepared, the former with both aniline and parachloraniline as diazo component giving yellows of good lightfastness in full shade but having poor llghtfastness in ZnO tints* Dimethyl cyclchexanedione coupled to parachloraniline formed a brown nickel compound <97$ purity) However, llghtfastness and bleed resistance (In oil) were poor. Other cyclic compounds such as 1,3 indandlone and 6-ethoxy thioindoxyl gave unsatisfactory results* Both were difficult to couple. The latter, when coupled to parachloraniline did net show evidence of metallization with nickel or copper* TOfflfifilfflfr to attempt was made to correlate the ratio of the enol-keto equilibrium of the various coupling components with the ability of the coupled products to metallize, using data obtained by the KurtMoyer brosination procedure* However, the facility with which metallization occurred did not appear to be related solely to the enolie contents thus obtained, although it may be significant that the reaction of 2,4- dihydroxy quinoline is quantitative and is used as an analytical method* furthermore, 5*5* dimethyl cyclohexane dione-1,3? which was successfully metallized, is reported to have a high enol value* The lack of correlation in other instances may have bean due to the use of alcohol as solvent in testing the com ponents while employing water as the medium for metallization of the corresponding dyestuffs* Beplaeement of water by ethyl alcohol or ethylene glycol, as thus suggested, did not give noticeably better results in instances where metallization was difficult. DUP050069285 In order to obtain the metal derivatives in purer form* some of them were extracted in a Sohxlet with benzene or acetone. All of those thus treated apparently contain unreacted dye or other soluble components, ranging in amounts from h.00 extracted from a laboratory sample of Green-Gold to 27*2% extracted from the nickel derivative of paracfeloraniline --> 5,5 dimethyl dihydro resorcin. Since this pigment was found by analysis to he '97$ pttre, the metal complex is evidently noticeably soluble. Actually all the extracts upon evaporation left residues which gave a strong test for nickel. Although some of the products were improved in tinctorial properties by extraction* better lightfastness and bleed resistance resulted in only a few instances. The following coupling components which were used were available in Jackson laboratory files or were obtained from chemical suppliers * Acetyl Acetone Benzoylacetone Dibenzoylmethane Ethyloxal acetate Aeetoaeetanilide Benzoylac etanillde 2*h Dihydroxy quinoline 2-Hydroxy-4-methyl quinoline 1,3 Isoquinolinediol 1-Phenyl~3methyl-5-pyrazolone Cyclohexanedlol-1,3. M* Dimethyl cyclohexanediol-1,3 -Indandione 6-Ethoxy thioindoxyl A number of intermediates were prepared by methods outlined in the literature, the details for which are to be found in If.B.1290. These included) H-Methyl aeetoaeetanilide B-Ethyl aeetoaeetanilide 2-Acetonyl benzimlnazole 2-Phenacyl benziminazole 2-Acetonyl benzthiazole U-Bydroxy-2-methyl quinoline 2fh-Dihydroxy-B-methyl quinoline Benzotetronic Add 7-nitro-2 ,V-dihydroxy quinoline Anilides of maleic and oxalacetic adds. For details of couplings and metallisations see N.B.1396. DUP050069286