Document nNRaXyZ7YxLYx6r9vR458MwB1

N37211 S e ria l Number 18706 | JLR-53-152, No. 2. Serial Number 18706 ;\ Dr. H. w. Elley Dr. E. K Bolton Dr. Wm . Kirk Mr. J. s. Groves for I .0.1. J. l . :Piles Mr. A. J. Wuertz (2) (1) (1) (3) ,, (2)<S (1) E. I. DuPont DeNemours & Company Jackson Laboratory October 11, 19-43 Please return JACKSON LABORATORY HUES Ponsol Khaki 2G Problem Report E. E. Beard M. S. Whelen H. R. Lee, Group Leader Written by - M. S. Whelen A. J Wuertz, Division Head JLR-53-152, No. 2. DUP050040696 Ponsol Khaki 2G (Project No.2259) M. S. Nhelen JLH-53-152, No. 2. Serial Number 18706, Object of the Investigation: 1 To prepare highly pure samples of pentanthrimide carbazole (Ponsol Khaki 2G) and tetranthrimide khaki (Caledon Khaki R) and to evaluate them versus Ponsol Khaki 2G and Caledon Khaki R. Period Covered by the Report; February 8, 1943 to August 30, 1943. Historical Background; The manufacture of Ponsol Khaki 2G was commenced in 1932 and since that time variations have always been encountered in the 'quality of the color produced relative to shade, strength, and fastness. Some of these variations were obviously directly related to the quality of the intermediate, especially 1:4:5:8-tetra-chloroanthraquinone which at times probably contains 1:4:5-tri-chloroanthraquinone, and gives rise to a mixture of tetra- and penta-anthrimide carbazole. It was accordingly deemed advisable to prepare highly pure samples of 1:4:5-triehloro-anthraquinone and 1:4:5:8tetra-chloro-anthraquinone and to convert them to the tetranthrimide carbazole (Caledon Khaki R) and pentanthrimide carbazole (Ponsol Khaki 2G), obtaining these products as pure as possible, and to compare and evaluate them versus the present standards. Conclus Ions *. y The object of the investigation was attained. Highly pure samples of tetranthrimide carbazole and pentanthrimide carbazole were prepared and submitted to the Technical Laboratory for evalua tion as preliminary samples J-53-F-57 and J-53-P-56, respectively. From the data obtained it has been shown that (l) highly pure Ponsol Khaki 2G is 20$ stronger tine torially, and is green*1 and brighter than the present standard Ponsol Khaki 2G, but its fastness properties are not improved, (2) that tetranthrimide carbazole is an equally good dyestuff, and from this it is concluded that its possible presence in Ponsol Khaki 2G by way of 1:4:5;-triehloroanthraquinone in 1:4:5:8-tetra-chloro-anthraquinone is not disadvan tageous . -1- DUP050040697 Summary: Tetranthrlmlde Oarbazole (Caledon Khalcl R) A highly pur sample of 1:4:5~trichloro-anthraquinone was pre pared and condensed with three moles of purified a-amino-anthraquin ; The resultant tetranthrimide was filtered from hot nitrobenzene and then converted to color by aluminum-chloride-sodium-chioride fusion and the color purified by acid oxidation followed by a partial vatting procedure. This material dyed much redder, trace duller, lOO/lOO, on equal solids basis, vs. Ponsol Khaki 2G Standard, Lot 325, and was a trace superior in bleach fastness, and trace to noticeably Inferior in light fastness versus this standard, Pentanthrlmide Carbazole A highly pure sample of 1:4:5:8-tetra-chloro-anthraquinone was prepared by subjecting good quality material to an acid and solvent .crystallization. This was condensed with four moles of purified a-amino-anthraquinone and converted to purified color in a manner analogous to that shown above. This material dyed 80/IOO, on an equal solids basis, much greener and noticeably brighter versus Ponsol Khaki 2G- standard. Lot 325, and was appreciably Inferior in bleach fastness and light fastness when compared to this standard. Patent Situation: No new patentable features are involved. Experimental: Purification of a-Amtno-Anthraqulnone a-Araino-anthraquinone as produced in the plant was suspended in five parts of nitrobenzene together with .0.1 parts of charcoal. The whole was heated to 1.50C. and held 3 hours and then filtered hot. The filtrate after standing overnight was filtered to remove the crystallized a-amino-anthraquinone, which was washed with .2 parts of nitrobenzene followed by .2 parts of alcohol. The cake was then slurried in 3-i/2 parts of alcohol, and the suspension filtered, after which the cake was washed with 0.2 parts of alcohol and dried. The recovery was ,8 - .85 parts. Chromatograph analysis of this product showed that almost all 1:2-diamino-anthraquinone impurity and some of the p-amino-anthraquinone impurity was removed. -2- DUP050040698 This solvent method of purification was found to be a more satisfactory method of purification than one involving crystalliza tion from 80$ sulfuric acid. JLNB-4088, pages 12/18, and 19. JLNB = Jackson Laboratory Notebook Purification of Plant Solvent Processed 1:4:5:8-TetraChloro-Anthraqulnone and Preparation of a Pure Sample 1 - Acid Purification 2.00 Grams 1:4:5:8-tetra-chioro-anthraquinone (solvent processed) and 1200 grams 100$ sulfuric acid (chlorine 39*50$, melting point 349-353C. ) were stirred together at 50C, for 3-1/2 hours, then for l/2 hour at 25C. The insoluble tetra-chloro-anthraquinone was filtered off, and the cake washed with 96$ sulfuric acid, after which it was slurried in hot water, filtered, washed and dried. Yield - 188 grams, which is a recovery of 94$. The filtrate was drowned, 4.4 grams of material Isolated. The purified material had the following analysis; Chlorine - 40.65$ - The theoretical chlorine content of l:4:5*8-tetra-chlo'ro-anthraquinone is 41.0$. M.P. - 351-354C. The material recovered from the filtrate, showed a chlorine Content of 15*93$ and a melting point of 268-307C. 2 - Solvent Purification A composite of 450 grams of acid-purified 1:4:5;8-tetrachioro-anthraquinone, purified as above, was dissolved at 215-220C. in 3125 grams trichloro-benzene. Crystallization was effected by stirring while cooling to 40C., and the tetra-chloro-anthraquinone was filtered off after standing overnight, after which it was washed with alcohol and dried. Recovery - 430 grams = 95*5$* Analysis - Chlorine, 40.72$, 40.96$ - M.P. 354.2-355C. JLNB-4083, pages 10 and 11. This material was used for all subsequent preparations of pentanthrimide. 3- - DUP050040699 Pentanthrimide To secure a high quality anthrimide It was necessary to filter it from the solvent and the following procedure was utilized. 22.5 Grams 1:4:5:8-tetra-chloro-anthraquinone, M.P. 354-355C. , Cl = 40,69$, 58.0 grams a-amlno-anthraquinone purified, 327.0 grams nitrobenzene, 25.0 grams soda ash, 3.0 grams copper acetate and 0.3 grams copper powder were heated at 205-208C. for five hours. The pentanthrimide was filtered from the solvent at 150C , and it was washed with nitrobenzene and alcohol, after which it was steamed, acidified with dilute hydrochloric acid, filtered, washed, and dried. Yield 62.1 grams (87.4$). The filtrate was steamed and 10.1 grams of material was recovered. Analysis for duplicate experiments were 1 - Nitrogen - 5.08$ - Chlorine - 0.54$ (On the residue 4.59$ - Chlorine 1.39$ 2 - Nitrogen - 5.00$ - Chlorine - 0.54$ (On the residue 4.63$ - Chlorine 2.08$ The theoretical content of nitrogen in pentanthrimide is 5,13$. " JLNB-4088, page 23. A further experiment, material from which was used to prepare pentanthrimide carbazole, gave a yield of 78.3$ of theory from tetrachloro-anthraquinone. Nitrogen 5.01$ - Chlorine 0.33$. JLNB-4059* page 100. Pentanthrimide Carbazole - Ponsol Khaki 2G Fusion 666 Grams aluminum chloride, 100 grams sodium chloride.dry were heated together to 1850. and over one-half hour at l85-195C . a mixture of 100 grams pentanthrimide and 40 grams sodium chloride dry was added, Heating was continued at l85~190C. for 10 minutes, after which the reaction mass was poured into cold water, stirred one hour, filtered and washed acid-free. Acid Oxidation The above cake of crude color was suspended in five liters of water, to which 600 grams of 96$ sulfuric acid had been added. To .this was added 85 grams of sodium dichromate, and acid oxidation -4* DUP050040700 was carried out for two hours at 85-90C., after which time sodium dichromate was still present. The color was then filtered off and washed acid free, and given the following alkali-treatment. Alkali-Treatment and Purification by a Vetting Procedure The crude dyestuff> prepared as above, was suspended in four liters of water and 90 ranis of sodium hydroxide, and 37 grams of sodium hydrosulflte was added at 55C. , which temperature was held l/2 hour. The insoluble color was filtered off and washed with warm water. The cake was then again suspended in four liters of water, 100 grams of sodium hydroxide was added; and the whole heated at 95C. for two hours. The color was filtered off while hot, washed free from alkali and made up to 720 grams paste with the assistance of leucanol. After milling, the extracted solids were 12.75$> equivalent to 91*8 grams of color or 91.8$ of theory from pentanthrlmide. The overall yield from 1:4:5:8-tetra-chloro-anthraquinone was 71.9$* On preliminary test this material dyed 80/100 on skeins, and 85/IOO on pads, much greener and brighter versus Ponsol Khaki .20 Standard, Lot 325- It was submitted as Preliminary Sample J-53-P-56 for evaluation, the results of which are to be found at the end of this report. JLNB-4059, page 102. 1:4:5-Trichloro-Anthraqulnone Preparation^of a Highly Pure Sample The method proposed was to nitrate a pure sample of 1-nitro-5chloro-anthraquinone, and then replace the two nitro groups by chlorine in trichloro-benzene. Purification of l-Nltro-5-0hloro-Anthraquinone 200 Grams 1-nitro-5-chloro-anthraquinone was stirred overnight . at room temperature in 1600 grams of 96$ sulfuric acid. The in soluble l-nitro-5-chloro-anthraquinone was filtered off and washed with 800 grams of 96$ sulfuric acid. It was boiled out in hot water, "titered and washed. Recovery - 166-5 grams which is $3.2$. Analysis - Chlorine - 12.77$ - The theoretical chlorine content of l-nitro-5-chloro-anthraquinone is 12.35$. Nitrogen - 4.63$ - The theoretical nitrogen content of 1-nitr0-5-chloro-anthraquinone ' is 4.87$. Melting Point - 308C. JLNB-4059, page 104. . ..5- DUP050040701 Nitration, of l-Nltro-5-Chloro-Anthraquinone 160 Grams 1-nitro-5-chloro-anthraquinone (purified) and 1000 grams 98-99# sulfuric acid were mixed and- cooled to 5C. and 42 grams of 96# nitric acid was added dropwise at 5-80. over one hour. The nitration mass was stirred overnight at room temperature and then heated to 40C. for one hour, after which it was drowned in cold water. The precipitated dinitro-chioro-anthraquinone was filtered off and washed acid free. Yield - l8l grams which is 97-3# of theory. Analysis - Chlorine - 10.97# - The theoretical amount of chlorine in dinitro-chloro-anthraquinone is 10.67#. Nitrogen - 8.13# - The theoretical amount of nitrogen in dlnitro-chloro-anthraquinone is 8.43#. Melting Point - 522C. JLNB-4059> page 106. Chlorination of Dlnltro-Chloro-Anthraquinone 178 Grams of dinitro-chioro-anthraquinone, as above prepared, was suspended in 1050 grams trichloro-benzene and heated to 200C. at which temperature chlorine gas was passed in slowly for l4 hours.' The trichloro-anthraquinone was filtered off after cooling, washed with ortho-dichloro-benzene to replace mother liquor, and the ortho-dichloro-benzene wet cake was redissolved by heating at 175C. in 800 grams of ortho-dichloro-benzene together with five grams of charcoal. Clarification was effected by filtering hot, and the 1:4.*5-trichloro-anthraquinone was allowed to crystallize by slow cooling with agitation, after which it was filtered off, and washed with ortho-dichloro-benzene and alcohol. Analysis - Chlorine - 34.65# - The theoretical amount of chlorim in trichloro-anthraquinone is Nitrogen - 0.01# 33-97#. JLNB-4059, page 106. Tetranthrlmlde Carbazole - Caledon Khaki B Te tranthrimlde 51.1 Grams l:4:5-trichloro-anthraquinone (m.P. 264G v), 66.9 grams a-amlno-anthraquinone purified, 450.0 grams nitrobenzene, 55..0 grams soda ash, 4.0 grams copper acetate, and 0.1 grams copper powder were heated together at 200-.205C. for 8 hours. The 6- - DUP050040702 temperature was then lowered to 150C., and after 8 hours the tetraanthrimide was filtered off, washed with nitrobenzene and then steamed. Yield - 88 grams which is 100$ of theory. JLNB-4059, page 110. Tetranthrlmlde Carbazole A melt consisting of 579 grams aluminum chloride and 87 grams dry sodium chloride was prepared by heating to 185C. and at 185190C. a mixture of 87 grams of tetranthrlmlde and.55 grams of dry 30dium chloride was added over 20 minutes, after which the fus ion was kept at 190-195C. for a further 10 minutes, it was cooled to l60C. and drowned in cold water. The crude dyestuff was filtered off and washed acid-free with hot water. It was subjected to acid oxidation by suspending the cake in four liters of j3rl0$ sulfuric acid containing 90 grams of sodium dichromate at 90-95C. for four hours. At the end of this period of heating, dichromate was still present. The dyestuff was filtered off, and washed acid free with hot water. It was then subjected to an alkali-vatting treatment, by suspending the cake in 4-liters of water, cbhtaining 50 grams of sodium hydroxide at 55C . 50 Grams of sodium hydrosulfite was added and a temperature of 550. was maintained for 1/2 hour, after which the dyestuff was filtered off, and washed alkali free with warm water. It was made up to 600 grams of paste with the assistance of leucanol having an extracted solids of 10.28$, which is equivalent to 6l.7 grams of dyestuff or 70,9$ of theory. The overall yield of dyestuff from trichloro-anthraquinone is 70.9$* After milling this product was submitted as- preliminary sample J-53-P 57 for further evaluation by the Technical Laboratory. JLNB-4059, page 114. After evaluation of the pentanthrimlde carbazole (Ponsol Khaki 2G) and tetranthrlmlde carbazole (Caledon Khaki R) the Technical Laboratory reported as follows, the following being taken from Memo. 1100-B. Summary Tests have been made where the samples J-53-P-56 and J-53-P-57 were substituted for Ponsol Khaki 2G Paste, Standard, in a typical O.L. No. 7 formulation. These tests showed so very little difference in fastness that no technical advantage or disadvantages over our present standard should be stressed. 7- - DUP050040703 Application Properties Coagulation Acid Alkaline Migration Khaki 2G Paste, Standard Khaki 2GP Paste, Standard P.S.A. #21790 (1.0,1,) P.S. 978, J-53-P-56 P.5. 979> J-53-P-57 Poor Poor Moderate Fairly go'od Moderate Poor to poor Moderate Fairly good Poor Fairly good Poor Moderate Poor Moderate Moderate to poor Shade and Strength - On Cotton Skeins - Vol. 20:1 Comparison of P.S, 978, J-53-P-56 with Ponsol Khaki 2G Paste, Standard, Lot 325. Shade - much greener, noticeably brighter Strength - 53:100 - 4.5 lbs. = 8.4 lbs. Exhaust - trace superior Comparison of P.S. 979, J-53-P-57 with Ponsol Khaki 2G Paste Standard, Lot 325: Shade - much redder, trace duller Strength - 95:100 - 8.0 lbs, * 8.4 lbs. Exhaust - trace inferior Comparison of P.S. 978, J-53-P-56 with Caledon Khaki RS Paste, P.S.A. No. 21790 Shade - much greener, considerably brighter Strength - 35:100 - 4,5 lbs. - 11,5+ lbs. Exhaust - noticeably superior Comparison of P.S. 979, J-53-P-57 with Caledon Khaki RS Paste, P.S.A. No. 21790. Shade - much greener, noticeably brighter Strength - 63:100 - 7.2 lbs. = 11.5 lbs. Exhaust - trace superior Solids P.S. 978, J-53-P-56 - 12.52$ Ext. A & E P.S. 979, J-53-P-57 - 10.08$ Ext. A &E P.S.A. No. 21790 - 11.9$Ext. A & E Khaki 2G Paste, Standard, Lot 325 9-4$ Ext. A & E -3- * DUP050040704 Fastness Properties Comparison of the fastness properties of the samples listed below, with those of a 12.6 oz./gal. padding of Ponsol Khaki 2G PasteStandard, Lot 325- 7.15 oz./gal. P.S. 978 J-55-P-56 11.5 Oz./Gal. P.S. 979 0.3$ Chlorine Appreciably Inferior One laundry wheel treatment Similar Five laundry wheel treatment Trace superior Scrubbing with soap 40 Hour Fade-Ometer exposure Similar Appreciably inferior 20 Day weather exposure 30 Day weather exposure Trace inferior Trace Inferior Trace superior Trace superior Trace to notice ably superior Trace superior Trace to notice ably inferior Noticeably inf. Trace inferior Comparison of the fastness properties of the samples listed below with those of an 18.4 oz./gal. padding of P.S.A. No. 21790, Caledon Khaki RS Paste (i.C.I.) 0.3$ Chlorine Appreciably inferior One laundry wheel treatment Similar Five laundry wheel treatment Similar Scrubbing with soap Trace inferior 40 Hour Fade-Ometer exposure Appreciably inferior 144 Hour Fade-Ometer exposure Appreciably inferior 20 Day weather exposure Noticeably superior 30 Day weather exposure Noticeably superior Similar Trace superior Trace superior Similar Trace inferior Trace inferior Noticeably sup. Similar Submitted for typing October 19, 1943 Typed October 30, 1943 Eleanore M, Zinck 9- - DUP050040705