Document rBYmmeG2rQjDwv4pv7MZwD6K7

' Return to: >t 'ti* .FILFFQOH Return to: J. L. fflLSROCW IfC' Beturc to: J> h. pix.aooii Betum to: 1780 J* l . Jitsfioai DUP050040740 } I, . 5-169, Wo. 1. Serial Number 18727 Dr, H. . Elley Dr. E. K. Bolton Dr. Wm . Kirk Mr. A, J. Vuertz for I. C. I. J. L. Files Dr . S. S. Rossander (2) (1) (1) (3) (2), (1) < sS MJ O CO S 5 Kd 2 0 m E,' I, DuPont DeNemours & Company Jackson Laboratory November 13. 19*13. Ponsol Brown VR Preparation of Purified Color l Progress Report Vm. Det.twyler H. R* Lee Group Leader S. S. Rossender Division Head DUP050040741 Ponsol Brown VR Preparation of Purified Color (Project Ho, 2370) Vim. Dettwyler JLR-53-169, No. 1. Serial Number 18727. Object of the Investigation: To prepare a sample of purified Ponsol Brown VR and compare its fastness properties with those of the present standard. Period Covered by Report: January 12, 1945 to April 2, 1945 His t or1ca1 Ba ckground; The present process for manufacturing Ponsol Brown VR utilizes intermediates of a rather crude nature and does not contain any steps in which the intermediates or the color are purified. The final color contains, therefore, an appreciable amount of impurities which are detrimental to the shade and fastness properties. Conclusions: The object has been attained. Two samples of Ponsol Brown VR were prepared which exhibited increased tinctorial power (dyeing 72:100 on an equal solids basis) and all-around superior fastness properties over the existing standard. Summary: ... The problem of preparing a sample of pure Ponsol Brown VR was attacked in two ways. 1 Crystallization of the plant product from sulfuric acid (overall yield 58$ of theory). 2 - Purification of the intermediates and isolation of the products at each step in the process thereby eliminating the accumulation of impurities in these steps. (Overall yield 85.9$ from purified 1:5-dichloro-anthraquinone and purified aminoacridone. Both methods gave color dyeing 72:100 vs. standard and having much improved fastness properties.) -1- DUP050040742 If ? 'Patent Situation: No patentable matter is contained in this report. Plena for Future Work: The work is being carried forward under J-55-35, a project which has as its main objective the preparation of pure 1-amino-8~ chloro-anthraquinone, which is the basic Intermediate for Ponsol Brown VR. The present quality of 1-amino-8-chloro-arithraquinone is low as it contains about 10# of the 1:5-isomer and about 10# of other Impurities not suitable for making Brown VR. Its purity largely determines the quality and yield of the final color. This phase of the investigation is essential for the establishment of a workable process for Ponsol Brown VR of improved quality and will be reported in a subsequent report. Exp er intenta i Results: I - Crystallization of the Plant Crude Color Fifty grams of Ponsol Brown VR plant crude was dissolved in 500 grams sulfuric acid. The solution was heated to 80C . and 126 grams of. water added at such a rate that the temperature did not rise above 90C. This gave an acid concentration of 80# in which the color was dispersed in the form of fine needles. The mass was cooled to room temperature and filtered on a glass funnel .The cake was washed with 200 grams of 80# sulfuric acid. The cake was dispersed in water, filtered and washed acid free. Yield - 19 grams = 58# recovery. JLNB-4008, page 105- This dry powder was dissolved again in 200 grams of mono- ' hydrate, diluted in water to give about 10# acid concentration and after adding 10 grams sodium dichromate heated at 95 for three hours. After filtration and washing 150 grams of paste was obtained, which dyed 72:100 appreciably yellower and brighter on an equal solids basis vs. the standard. A summary of the fastness tests of this sample (X-5755 cake) and the second sample (X-5760) are attached. % DUP050040743 2 - Brown VR Made Prom Purified Intermediates A - Purification of 8-Amlno-Anthraqulnone-2:1-Benzacrldone 100 Grams 8-amino-anthraquinonc -2:1(N) -benzacridone (plant material) was dissolved at 55-60C, In 1000 grams sulfuric acid 96%. 750 Grams of water was then added at such a rate that the tempera ture rose to 75"800. The resulting acid concentration was 55%. The 8-amino-acridone crystallized out in brownish spearhead-like crystals. After cooling to room temperature they were filtered off and washed with 500 grams 50$ sulfuric acid. The 8-aminoacridone is slightly soluble in 50% sulfuric acid. The cake was diluted with hot water, filtered and washed acid-free. Yield = 75 grams - 75$ recovery. JLNB-4008j page 88. Nitrogen - 1.65% - Theory 8,25% Melting Point - 388C. B * Purification of 1:5-Dlchloro-Anthraqulnone 100 Grams 1:5-dichloro-anthraquinone, plant charge 253, -Cl - 25.08$, M.P. = 245~46<>C, were dissolved in 500 grams orthodichloro-benzene at the boll and after the addition of ten grams of FilterrCel the boiling solution was filtered. On cooling the 1:5-dichloro-apthraqulnone crystallized out in greenish-yellow needles, which were filtered off and washed with 100 grams dichloro benzene and then with alcohol until free of solvent. JLNB-4008, page 87. Yield - 78 grams = 78.0% recovery. Cl = 25.62% Melting Point = 248C. C - Condensation 20,5 Grams of 1j 5-dichloro-anthraquinone (from B)> 50 grams 8-amino-anthraquinone-2:1(N)-benzacridone purified (from A), 15 grams soda ash and 1.5 grams cuprous chloride were heated in 700 grams nitrobenzene at reflux temperature for 16 hours. After cooling to room temperature, the condensation product was filtered off and washed with 300 grams nitrobenzene. The cake was steam distilled free of nitrobenzene, filtered and washed alkali free and dried, JLNB-4008, page 97. Yield - 63 grams = 97.5$ of theory. -5- ' . DUP050040744 D - Ring-Closure 1 40 Grams aluminum chloride (freshly ground) were dissolved in 100 grams nitrobenzene and 25 grams- of the above "anthrimide" added, The brown solution was heated at 130-135C. for 5 -hours, poured into one liter of cold water and steam distilled free of nitrobenzene, filtered, washed and dried. JLNB-4008, page 110. Yield 34 grams dry Yield 136# contains nitrobenzene-A1C1_ reaction product. E - Crystallization of Color 34 Grams of above crude color were dissolved in 300 grams mono-hydrate at 75-80 and 128 grams water added at 80-90C. This reduced the acid strength to 70$. After cooling the mass to room temperature it was filtered and the cake washed with 200 grams 70$ acid. The cake was diluted in water, filtered and washed acid free, JLNB-4008, page 110. Yield = 22 grams * 65$ yield, P - Pasting This 22 grams of pure dry color were redissolved in 200 grams mono-hydrate, the solution diluted into cold water to give about 10$ sulfuric acid, 10 grams sodium dichromate added and heated at 95C. for 3 hours. The suspension was filtered, washed acid-free and the paste milled with enough water to give 200 grams paste, ` JLNB-4008, page 110, It dyed 72:100, much yellower and brighter than standard. Attached is the report of the Technical Laboratory oh the fastness properties of the two samples vs. the standard. 4- - DUP050040745 SALES DIVISION TECHNICAL LABORATORY Date - 2-12-45 Charge - J-15-9 Department - Vat Colors No. 553 D. S, or P.S. No. Name of Product or Shade; Brown VR - 5755-B cake - 12.5$ solids 5760 - 11.0$ solids Tests to be made Please dye vs. Ponsol Brown VR. preliminary fastness tests. Include exhaust and make Date Received 2-15-45 REPORT Date Reported 2-25-43 Dyetest Report Solids Basis 100 parts Ponsol Brown VR Paste Standard 72 Parts 5755-B - appreciably yellower, trace brighter 72 Parts 5760 - much yellower, trace brighter The exhaust of Sample 5755-B Is trace to noticeably superior, that of 5760 a trace superior to that of Ponsol Brown VR Standard. Coagulation Acid Alkaline Standard Fairly good 5755-B Very poor K760 Very poor Poor Very poor Very poor Migration Poor Good Very good Fastness properties versus that of an 8.0 lb. dyeing of Ponsol Brown VR Paste. 0,3$ Chlorine - 6.35 Lb. 5755 - appreciably superior 7*23 Lb. 5760 - appreciably superior 0.7$ Chlorine - 6.35 Lb. 5755 - appreciably superior 7.23 Lb. 5760 - appreciably superior Alkali treatment 4 hours at 160F. without Sitol 6,35 Lb. 5755 - appreciably superior 7.23 Lb. 5760 - similar 5- - DUP050040746 Alkali treatment 4 hours at loO F. with Sltol 6.55 Lb* 5755 - similar 7.25 Lb, 57^0 - trace inferior Peroxide Bleach A - 6,55 Lb. 5755 - appreciably superior 7.25 Lb. 5760 - similar Peroxide Bleach B - 6.55 Lb, 5755 - appreciably superior 7.25 Lb. 5760 - similar Washing at l6oF. - 6.55 Lb. 5755 ~ similar 7.25 Lb. 5760 - similar One Laundry Wheel Test - 6.5 1 Lb, 5755 - similar 7.2 . Lb. 5760 - similar Five Laundry Wheel Test - 6.55 Lb-. 5755 * similar 7.25 Lb. 5760 - similar Light Fade-Ometer - 6.55 Lb. 5755 - appreciably superior 7.25 Lb. 5760 - appreciably superior - ] i Submitted for typing November 22, 1945 Typed December 16, 1945. emh 6- - 3f DUP050040747