Document 6R7e4V0yjJ0wwMvdZrN6ZQ3em

Dr. I. Gubelmannl Dr. H. A. Dubs J Dr. E. K. Bolton Dr. William Kirk Mr. J. S. Groves for I.C.I. J. L. Plies (1) (1) (1) Ji (3) / (2) E. X. DuPont de Wemoura & Company Jackson Laboratory May 25, 1942 DuPont Naphthanll Prangs GC 50 Base -Chlor-aniline-hydrochlorlde + maleic acid) N40785 JLR 38-57, No. 1 Serial Number 18054 B. I. DuPont de Nemours & Company Jackson Laboratory Azo Colors Division S. 3. Rossander Progress Report DuPont NaPhthanil Orange 00 50 Base (meta-Chlor-anillne-hydrochlorlde + maleic acid) Group Deader - 0. E. Sparks Work Done By - C. W. Maynard, Jr. 3. B. Smith C. E. Sparks Reported By - C. I. Sparks Work Started - March 1, 1941 Completed - May 1, 1942 J. M TINKER ASSISTANT DIRECTOR W. S. CALCOTT DIRECTOR DUP050059076 DuPont Naphthanll Orange 00 50 Base (Pro.leet Humber 2165) 0. E. Sparks JLR-38-57* No . 1 Object of the Investigation: Serial Number 18054' To develop a Naphthanll Orange GO 50 Base vhlch possesses satisfactory storage stability and printing paste stability. Period Covered by the Report; March 1, 1941, to May 1, 1942. Historical Background: Lot 1 of DuPont Naphthanll Orange GO 50 Base (1500 pounds) was found to be satisfactory by our Technical Laboratory versus Jackson Laboratory Final Sample J-38-F-106. After approximately 2 and l/2 months' storage at the Technical Laboratory (tempera ture 75-80*F.), it was noted that the sample had deteriorated slightly due to the presence of an insoluble product in the diazo solution Material stored in the shipping house (tempera ture about 50-55F. ) was found to be satisfactory with only a trace decomposition. Titration of the deteriorated sample to standard nitrite indicated no noticeable decomposition. In view of the difference in the decomposition rates between the material stored in the shipping house and at the Technical Laboratory, it was requested that the Naphthanll 50 Bases be stored in the coolest possible place at the Dye Works. (See letter of February 24, 1941, of C. E. Sparks to J. J. Carrigan.) It was decided, however, that Jackson Laboratory should attempt to obtain an Orange GO 50 Base which is stable to storage. In order to accomplish this, a special project J-38-57 was taken out for this work. This report summarizes the work done in this connection. Conclusion: A completely satisfactory DuPont Naphthanll Orange GC 50 Base with reference to storage stability and printing paste stability has not been found. Summary: DuPont Naphthanll Orange GC 50 Base (meta-chlor-anilinehydrochloride + maleic acid) deteriorates slowly on storage at -1- DUP050059077 room temperature; a reaction taking place which, on the basis of-, chemical analysis appears to be the formation of a maleate of meta-chlor-aniline of a molar ratio of 1.56 meta-chlor-aniline to 1 of maleic acid, this reaction product is insoluble when Orange GO 50 Base is diazotized. The decomposition of Orange GC 50 Base after 16 months' storage on the Dye Works cannot be determined by nitrite analysis. No satisfactory method of pre venting the reaction of meta-chlor-aniline with maleic acid has been found. The cloudy appearance of the diazo of Orange GC 50 Base which has been stored for several months at room temperature does not in any manner change the shade and strength on printing of the product. Patent Situation ; A patent application has been filed (Bossander, sparks, and Maynard Case I - Serial Number 558,296) which protects Naphthanil Orange GC 50 Base. No additional patentable material has been discovered in the investigation reported herein. Plans for Future Work; Work will be concentrated on obtaining a satisfactory Naphthanil Blue B 50 Base and leads obtained from this investiga tion will be applied to the Orange GC 50 Base, since the possible sales of the latter product are small as compared to the Blue B 50 Base. Also the storage stability of Blue B 50 Base is very much inferior to the Orange GC 50 Base. Experimental: The experimental work covered during the period of this report can be found recorded in the following Jackson Laboratory Notebooks? 5^56, 5504, 5556, 5654, 3845, 5648. Nature of the reaction between meta-chlor-aniline hydrochloride and maleic acid The reaction occurring between meta-chior-aniline-hydro chloride and maleic acid proceeds with very slow velocity at room temperature. Storage of Lot 1 of Naphthanil Orange GC 50 Base (mixed in December, 19^0) until April, 19*12, at room temperature contained a very small amount of insoluble matter -2- DUP050059078 matter in the dlazo solution. Prom 800 g, of such material there was obtained only 7 g* of insoluble matter whose analysis showed it to be a mixture of meta-chlor-aniline maleate of molar ratio 1.56 meta-chlor-aniline to 1 maleic acid. There was no tltratable loss of diazotizable meta-chlor-aniline during this 16 months' storage of Lot 1 at domestic shipping house. The only noticeable change was the development of a small amount of tur bidity in the dlazo solution. The shade and strength of Lot 1 are satisfactory versus a specially prepared fresh mix. It has been definitely shown that heat accelerates this reaction. Preliminary tests indicate that moisture also accelerates the reaction. The presence of maleic anhydride definitely accelerates the reaction. Substitute for Maleic Acid In order to obtain an Orange GO 50 Base which was more stable to storage, certain materials were investigated as pos sible substitutes for maleic acid. The following table summar izes briefly the reagents tried in this connection* TABLE I Substitutes for Maleic Acid in Naphthanil Orange GC 50 Base (Orange GC Base + diluent 1:1) Substitutes Printing Paste Stability Oven Stability at 50*0. 1-Sulfo-naphthalene heavy shades - 5 light shades - 1 1 -Sulfo -naphthalene potassium salt heavy shades - 4 light shades - 3 Mixture of p-tolyl-sulftoluene and maleic acid 1:1 4 Inferior 3,5-Dlsulfo-nitro-benzene + maleic acid 1:1 4 Inferior 2,7-Disulfo-naphthalene sodium salt + maleic acid 1:1 4 Inferior 1,3#6-Tris ulfo-naphthalene sodium salt + maleic acid 1:1 Inferior Sugar + maleic acid 1:1 5 Inferior KagSO^ + maleic acid 1:1 5 Sli. superior* * Sodium acid maleate ppts in diazotization. -3- DUP050059079 Codes 5 - equal to standard 50 Base 4 - slightly inferior to standard 50 base 1 - inferior to Orange GC Base See JLR-5S-D, Bo. 21; S.B. 17985 and JLR-58-V-25, Bo. 1 for reagents other than maleic acid which have been evaluated as printing paste stabilizers for DuPont Baphthanil Orange GC Base, me ta-Chlor-anillne-sulfate A sample of meta-chlor-aniline-sulfate was prepared by the reaction of sulfuric acid (monohydrate) on a toluene solution of me ta-chlor-aniLine, The resulting precipitate was filtered and dried. Mixtures of meta-chlor-aniline-sulfate and maleic acid were evaluated in the Baphthanil 50 Base versus Baphthanil Orange GC 50 Base (meta-chlor-aniline-hydrochloride + maleic acid). Storage stability tests indicated that the sulfate had no advantage over the hydrochloride for stability and was equal in printing properties both for shade, strength, and printing paste stability versus the standard 50 base, The effect of moixture upon the decomposition of DuPont Baphthanil Orange GC 50 Base Samples of Orange GC 50 Base containing a small amount of water (2-5#) were found to decompose quite rapidly when stored in an oven at 50C. Samples of Orange GC 50 Base prepared by mix ing (5 and 10#) partially dehydrated aluminum sulfate, anhydrous magnesium sulfate, and Zelan A with maleic acid and meta-ohloroaniline hydrochloride showed no advantage in storage stability over the standard mix. Effect of reducing agents on Orange GC 50 Base Samples of Orange GC 50 Base containing 5# sodium hydro sulfite were stored, stoppered, and unstoppered, at 50*C. and at room temperature. Storage tests indicated that the effect of sodium hydrosulfite on the stability of Orange GC 50 Base was negligible. It will be noted from the above results that we are not clear as to exactly what promotes the reaction between metachlor-aniline -hydrochloride and maleic acid. It is believed DUP050059080 that moisture and heat are the two greatest accelerating agents. We do not believe that the storage stability of Orange GO 50 Base is sufficiently serious to be too much concerned with at the present time in view of the small sales. Work on the 50 Base problem is to be concentrated on the preparation of a satisfactory Blue B 50 Base for the time being, hoping that information ob tained may be transferred to Orange GO 50 Base. Submitted for Typing - June 3, 1942 fmb July 9, 1942 -5- DUP050059081