Document 2RyNrKar36QkY5gLbKg6e27Dg

S e ria l Number l8 0 l8 JL p t /J Dr. X. Gubelmann Dr. H. A. Lubs _ Dr. E. K. Bolton Dr . William Kirk Mr. J. S. Gloves for I.G.I. J. L. Piles E. I. DuPont de Nemours & Company Jackson Laboratory July 20. 1942 1k J L R -3 8 -A , N o, 1)-9 New Naphthanlls ! N40779 JLR-38-A, No. 94 Serial Number 18018 I. DuPont de Nemours & Company Jackson Laboratory Ago Colors Division S. S. Rossender Progress Report July gO, 1942 Nev Nanhthanlls Group Leader - C. E. Sparks Work Done By - L. Spiegler 0. E. Sparks Reported By - 0. E. Sparks Work Started - 12-10-41 Completed - 5-15-42 J. M. TINKER ASSISTANT DIRECTOR W. S. CALCOTT DIRECTOR DUP050058997 New Naphthanlls (Project No. 608) C. E. Sparks JLR-58-A, No, 94 Object of the investigation: ' Serial Number 18018 To prepare new 2,3-hydroxy-naphthoyl derivative s of arylamines and to evaluate the same in Naphthanil colors. To prepare arylides of citrazinic acid-mono-butyl -ether and evaluate the same in Naphthanil colors. To prepare arylides of substituted salicylic acids and evaluate the same in Naphthanil colors. To prepare an anilide of a substituted salicylic acid which possesses the same apparent oxidation potential as Naphthanil AS and to evaluate the same in Naphthanil colors. Period Covered by This Report: December 10, 1941, to May 15, 1942. Historical Background: There is considerable need in our line of Naphthanlls at the present time for products which possess excellent substantivity and produce bright shades of excellent fastness properties when coupled with our standard Naphthanil bases. It is the policy of the laboratory to prepare 2,3-hydroxy-naphthoyl derivatives of arylamines as they become available with the hope that some coupling component of interest might be obtained. It has been suggested (letter of M. A. Dahlen to S.S.Rossander, dated 10-10-41) that citrazinic acid derivatives be investigated as Naphthanil coupling components. It has been suggested that it may be possible to prepare derivatives of arylides of salicylic acid which would be of interest in Naphthanil colors by the introduction of various groups into the salicylic acid ring. It was also suggested that, if the anilide of substituted salicylic acid possessing the same apparent oxidation potential as Naphthanil AS were evaluated, it might show promise in Naphthanil colors, -1- DUP050058998 Summary and Conclusions? No new arylides of 2-hydroxy-5-naphthoic acid have been obtained which show promise . Naphthol AS-KR Supra (BON of cresldine) is termed of no interest at present for possible addition to our line. The anilide and dianisidide of citrazinic acid-mono-butylether are of no interest due to poor fastness properties of the combinations with standard Naphthanll bases. Several arylides of substituted salicylic acid have been prepared and evaluated. None are of interest. The anilide of 2-hydroxy-4,5-dimethyl-benzoic acid possesses approximately the same apparent oxidation potential as Naphthanll AS. The product upon evaluation with standard Naphthanll bases is of no interest due to poor fastness properties. Patent Situation: No products have been prepared during the period covered by this report Which show sufficient merit to warrant patent protection. Plans for Future Work: We shall continue to prepare 2,5-hydroxy-naphthoyl deriva- . tives of arylamines as they become available in the laboratory. We plan no additional work on derivatives of citrazinic or salicylic acids as Naphthanll coupling components at this time. Wien times become normal# the question of preparing additional derivatives of salicylic acid will be reopened* Experimental Work? See Jackson Laboratory Notebooks >628, 5766* 5727* 5855* and 5778. The 2,5-hydroxy-naphthoyl derivatives reported here were prepared by the conventional methods* using toluene as a sol vent* an arylamine and PCI, as the condensing agent. The prod ucts were purified by isolation in toluene suspension and subse quently redissolving and purifying. The following table summarizes the products prepared and their properties. For details. 2- DUP050058999 as to the preparation of any specific product, please consult the corresponding JLNB. Where fastness tests are reported, they represent average results in couplings with Bordeaux GP, Scarlet 2G, Scarlet R, Orange GO, Blue B, Red B, Red AL, Red RO, Garnet GBC diazos. TABLE I JLNB r:z==s=rz==s=:x:=rss=srca=r==rs=asssxs?5 Mono or di BON Purity hy of Nitrogen 3727-120 p-Amino-phenoxyacetamide 3778-50 Ore sidine 3778-61 3- (4-Me thyl-sulfone-benzoylamino)-aniline 97.4# by sulfur isxssarassssasa:'a:s:ss.a:s:s593s.sxts:sss:s:asr Remarks Product of no interest due to extremely poor chlorine fastness* Washing fast ness of most combinations inferior to standard. Duplicates the dyeing properties of Naphthol AS-KR Supra* The Tech* Lab. completely evaluated this sample and found it to be of no interest with reference to addition to our line. See JLR-38-X, No. 39 for the identifica tion of Naphthol AS-KR Supra * This product was prepared by the condensation of 4methyl-s ulfone-benzoyl chloride on the mono BON of meta-phenylene-diamine. The product was found to be inferior in chlorine and light fastness versus Naphthanll BM, the most promising combinations being the same as those found with Naphthanil BM. It was suggested that several derivatives of salicylic acid be prepared and the anilide and dianisidide of these products be -3- DUP050059000 evaluated as Naphthanil coupling components. A series of these products vas prepared by L. Spiegler of the New Products Division and submitted to the Azo Division for evaluation. She general method employed for the preparation of these arylides is graphically represented as follows! 3R0H-C00H + ^RNHg.HCl + PClj --compounds + H^PO^ + 6HC1. The procedure employed is described in TT.S. Patent 1,690,201 (1932) DuPont. After the condensation and removal of solvent by steam distillation, the products are isolated by filtration. The crude products are purified by repeated digestion with di lute sodium carbonate solution and with 2B alcohol. Yields shown are based on the salicylic acid derivatives employed. The AOP values (apparent oxidation potential) were deter mined by the Analytical Division from aqueous solutions at a pH of approximately 10-11. The anilide of 2-hydroxy-^,5-dimethylbenzoic acid possesses approximately the same AOP (900) as Naphthanil A3 (890). The product upon evaluation with representa tive Naphthanil Bases shows very poor soaping fastness with the exception of the Scarlet 20 and the Blue B combinations. These combinations, however, were found to be considerably inferior in light fastness versus combinations producible by components on the market. We have been unable to correlate the AOP values and dyeing properties of Naphthanil coupling components. No further work is planned in this connection. The following table summarizes the salicylic acid derivatives prepared and evaluated during this reports TABLE II ,s:sss9sssss:s8s:5s^.;s'*ss-:ss3s.te.!5:s:s.8.ss^ JLNB Name Percent age Yield Purity by Nitrogen Analysis AOP Remarks 3628- Anilide of 2-hy 139 droxy-5 -me thyl benzoic acid 90 99 -4- Weak brown shades of poor fastness properties with representative Diagen bases and std. Naphthanil Bases. Bee JLNB 3727-86 and 377824. DUP050059001 JLNB 5628143 Name Anilide of 2-hy droxy-3-me thylbenzoic acid 3628- Dlanisldide of 2145 hydroxy-3-roe thylbenzoic acid 5628- 147, 151 Anilide of 2-hydroxy-benzoylamino-benzoic acid 3628- Dianisidide of 5149 methyl-2-hydroxybenzoic acid 362$157 Dianisidide of 5benzoyl-amino-2hydroxy-benzoic acid 3628* Dianisidide of 5159 nitro-2-hydroxybenzoic acid Purity Percent by age Nitrogen Yield Analysis AOP Remarks 88 100 Very weak prints were obtained in combination with representative Diagen bases.See JLNB 3778-32, 81 93 Very dull and weak prints with representative Diagen bases.See JLNB 3778-32. 64 99 Weak brown shades were obtained with poor fastness properties with representative Diagen bases.See JLNB 3727-176. 23 81 Sample possesses very poor solu bility in the printing paste. Weak brown shades are obtained which were of no interest 7*5 97 Weak brown shades which are of no interest are pro duced with repre sentative Diagen bases. See JLNB 3727-176. 69 87 Solubility of this sample is extreme ly poor and could not be printed satisfactorily. Product is a very weak coupler and is of no Interest for dyeing. See JLNB 5727-176. DUP050059002 JLNB Name Percent age ________Yield Purity by Nitrogen Analysis AOP Remarks 5628- Benzldlde of 2-hyl6l droxy-5-me thylBenzoic acid 50 95 * Weak brown shades are produced with representative Dlagen bases. Product is of no interest for dye ing. See JLNB 3727-176. 5628- Tolidlde of 5-meth3d-0- 55 165 hydroxy benzole acid 9^ - Same as above. 5628- 5-(4 -Ni tro-phenyl177 azo) - 2 -hydroxy-ben zoic acid 58 93 - Poor coupling com ponent . Prints obtained were weak and dull with very poor soaping fast ness. Dyeings were of no interest be cause of weakness ' and poor fastness properties. See JLNB 3778-32. 3628- Benzldlde of 5-(4- 179 nltro-phenyl-azo)- 2 -hydroxy-benzoic acid 52 87 - Product a very poor coupling com ponent and prints and dyeings are weak browns of no interest. See JLNB 3778-32. 3628191 3766- 9 Anilide of 5-chlor2-hydroxy-benzolc acid 82 98 - Sample possesses very poor solu bility for print ing. Dyeings are of no interest due to weakness and poor fastness properties. See JLNB 3778-32. -6- DUP050059003 JLNB Name 5766'- Benzidide of 5* 3 chioro-hydroxybenzoic acid 3766- Dlanisldide of 2- 111 hydroxy-4,5-di me thyl -benzolc acid 3778135 3766113 Anilide of 2-hydroxy-4,5-dimethyl-benzoic acid 3766- Anilide of 5-me125 thoxy-2-hydroxybenzoic acid Percent age Yield 2 57 69 Purity by Nitrogen Analysis AOP Remarks 100 - Very poor coupling component* Very weak tints obtain ed which are of no interest* Dyeings of no interest* JLNB 3778-32. 90 851 Product shows good coupling proper ties but weak brown shades of no interest are obtained. 96 900 Product possesses approximately the same AOP as Naphthanil AS (890). Weak dye ings obtained which possess poor soaping fastness with the exception of Scarlet 20, and Blue 8 Bases. These two products are of no interest vs. close approxi mations from stand ard combinations, in view of inferior fastness properties, 98 780 Product possesses good coupling prop ertie s,but is of no interest due to poor soaping fast ness in combina tion with standard .bases. JLNB 3853- 22 -7- DUP050059004 JLNB 3766127 Name Dianisidide of 5methoxy-2-hydroxybenzoic acid Purity Percent- by age Nitrogen Yield Analysis AOP Remarks 58 90 828 Product of no intereet due to poor fastness properties in com bination with std. bases. JLNB 3853- 22. .assssrs9^^.as9.ss;ss:ssxS8ssatS8Sttss99Ss.8B.s.s:.is.l8.s:s:s.s&.ss;s;.S8'S99'^9.ts9s9lS?'Ss?S'8S'a;ssas:.isft In the above table under Remarks the phrase, "representative Diagen Bases" includes: Diagen A bases of 4-chloro-2-aminotoluene and 4-chloro-2-amino-anisole, Diagen MG Bases of cresldine and dianisidine and the dlasoiminos of Scarlet R and Red B bases with 2-ethylamino-5-sulfo-benzoic acid. It will be noted from the above table that no products show promise as Naphthanil coupling components being either poor couplers, weak tinetorially or giving dull shades of no interest with inferior fastness properties. No further work in this connection is planned. In order to prepare the arylides of hydroxy benzoic acids above listed, it was necessary to prepare certain carboxylic acids which were not available at Jackson Laboratory. The fol lowing table summarizes these acids: TABLE III JLNB 3628-141 3628-155, 167 3766-21 3766-115 Name ______________ 2-Hydroxy-5-me thyl-benzoic acid 2-Hydroxy-5-chloro-benzoic acid 2-Hydroxy-4,5-dimethylbenzoic acid 2-Hydroxy-5-me thoxy-benzolc acid Yield 80 96 90 60 AOP 1042 1040 1100 840 -8- DUP050059005 Melting points were obtained on tbe above compounds and found in each case to check with that of the literature with in experimental error. The salicylic acid derivatives listed above were obtained by carbonatlon of the dry powdered sodium phenolate at 100-170C. at 500 pounds C02 pressure. Yields above are based on the phenolic compounds employed. AOP Values The apparent oxidation potentials (AOP) in the two tables listed above were made of aqueous alkaline solutions of pH's between 10 and 11 by the Analytical Division. Comparisons are listed below of AOP values for a number of typical coupling com ponents normally employed for the production of azo colors. Com pounds are listed in approximate order of their ease in coupling. Those considered to be the best couplers are at the top of the list. TABLE IV Name Resorcinol Phenyl methyl pyrazolone B-naphthol 6-hydroxy-naphthoic acid Naphthanll AS 4-Hydroxy-1,2-dimethyl-benzene ortho-Cresol para-Cresol Phenol para-Chlor-phenol Salicylic acid ortho-Cresotinlc acid AOP (10 to 11) in water 784 714 858 762 890 8ll 853 857 877 894 1043 1056 It is noted from the above table that within the same series (benzene or naphthene) the AOP is somewhat of a measure of the coupling speed. Miscellaneous Coupling Components The following table summarizes miscellaneous coupling com ponents evaluated during the period covered by this report: -9- DUP050059006 TABLE V BBSsSseasssareae:ssessS3sa=SBSBsaasnr=ssBSBSssaassss!:se=s=es=33 JLNB Name Remarks 3778-20-A N-methyl-triacetoneamine Prepared by W. S. Struve, JLNB 3607-89-B. Product of no in terest due to weak prints ob tained. 5778-20-B Triacetone amine hy drate Prepared by W. S. Struve, JLNB 3607-88-B. Product of no in terest in printing. Weak shade; obtained with standard Diagen bases. 3778-86 Dianisidlde of citra- (Purity 94# by nitrogen analy zinic acid mono-butyl- sis). Combinations with stand ether ard diazos show poor soaping fastness. Of no interest. 3853-38 Anilide of citrazlnic acid mono butyl ether Purity - 96$. Combinations with standard diazos are of no interest due to poor soaping fastness. 3727-22 2,4,6-Tri-(4-hydroxy1-naphthyl)-trlazlne Prepared by L. J. Conrad, JLNB 3675-5 Product gives dull shades of inferior fastness properties versus Naphthanils in our line. aa.8taaBsaaa3esseaaaas;ass>ass:sas3>aa:aa:.ss:s!S'sa:3smBS.asas8ss3:8a3:asfsi3aas:aaaas^aas:aeaa3a3s3seeaa)B3saBae As noted in the above table, none of the above products are of interest* The Preparation of Naphthanil AS Without the Use of Phosphorus Trichloride The New Products Division has synthesized Naphthanil AS without the use of phosphorus trichloride. (See JLR-38-A, Wo. 93.) The most promising samples were evaluated versus Naphthanil AS in dyeing - these samples were prepared by the reaction of acetanilide and BON in the presence of ortho-dichlor-benzene, by the reaction of BON and acetanilide in the presence of xylidine, and by the reaction of BON, aniline in the presence of acetic acid. These products were found to be essentially equal -10- DUP050059007 to Naphthanil AS in shade and fastness properties vhen ooupled with Naphthanil Scarlet R Base. However, the products showed very poor solubility and required approximately three times the normal amount of alcohol for solution for the preparation of the pads. For this reason the products were considered of no interest. Attempts to improve the solubility of these products by the method employed for the standardisation of Naphthanil AS failed. Submitted for typing - July 28, 1948 fmb August 27, 1942 -11- DUP050059008