Document 8R3ea4KyLr2LXXbgNoZ9d5DMo

JLR-^3-168, Wo* 8 Serial Humber 18715. * > <sc # 0 . Dr. H, W. Elley *** Dr. E. K, Bolton Dr. William Kirk Mr. A. J. Wuertz for I.C.I. * J. L. Files Dr. C. E. Sparks 3 =i z0 w=trs 0 <jt'4 1. I. DuPont de Nemours & Company (2) (1) (1) (1) Jackson Laboratory October 15> 19^3 Pontachrome Flavine A Problem Report B. G. Carson C. E, Sparks Division Head N37213 Pontachrome Flavine A (Project Number 1315) B. G. Carson jLR-45-168, No. 8 Serial Number 18715 Subject: ` Pontachrome Flavihe A (azo salicylic acid). Object of Investigation; (a) To recheck the laboratory and theoretical yields for Pontachrome Flavine A 125$, (b) to determine the cause or causes for the low hydrolysis yield of this color, and (c) .to make recommendations to the plant which would enable this yield to be improved. Period Covered by Report: May 22, 1942 to July 8, 1942; then intermittently to January 25, 1945. Historical Background: Pontachrome Flavine A (azo salicylic acid) has been known since 1914 when it was developed as Eriochrome Flavine A by Geigy and disclosed in German Patent 278,615; British Patent- 22,070 (1914) and United States Patent 1,157,169. A process ' for its manufacture was developed in Jackson Laboratory in 1955. Subsequent manufacture of this dye in the Semi-Works and the Dye Works indicated that the over-all yield from phthalic anhydride to Pontachrome Flavine A was very low, but the total amount of the color needed for the trade each year was so small as not to warrant further process work. Early in 1942, however, the need for large quantities of this dye for use in Army olive drab mixtures made it necessary for the yields in the various areas involved to be studied. It was found that the greatest loss occurred in the Basic Colors Area where the final hydrolysis of the product ...... - COOH COOH . -1 DUP050040725 was carried out. The standard Dye Works yield for this hydrolysis is 77$. The actual yields for January and February of 19^2 were very much below the standard yield. Conclusions; The primary objects of this investigation have been accomplished, (a) The laboratory yields previously reported in JLR-*K5-l68, Number 1, Serial Number 15015 have been confirmed; hydrolysis of the order of 92-95$ based on dyetest and on analyses can be obtained consistently in the laboratory. The theoretical yield is 7^0 pounds Pontachrome Flavine A, 125$ per mole of Pontachrome Flavine A Base, (b) 1. The main cause for failure of the hydrolysis has been shown to be the presence of lead in the hydrolysis autoclave; (the Dye Works autoclave used for this hydrolysis has a poured lead gasket which must be replaced frequently on account of failure) large amounts of lead reduce the dye stoichiometrically, small amounts appear to hinder the hydrolysis all out of proportion to the amount of lead present. The exact course of the reaction in the presence of small amounts of lead has not been determined. 2. The condition of the walls of the autoclave has an appreciable effect on the yield from the hydrolysis. When the iron-walls are clean almost no hydrolysis occurs; when the walls have been conditioned by several (or many) runs good yields may be expected. 5. The hydrolysis reaction does not appear to depend on the presence of a copper catalyst, but better yields are obtained if copper in some form is used. (c) It has been recommended to the plant that the lead gasket in the hydrolysis autoclave be replaced with one fabri cated from copper, corrugated iron with asbestos filling or asbestos. On account of complete failure of the lead gasket, for the third time in seven months, a change has been made. In the meantime the plant yield had risen to 8l$ of theory. Some of this may be attributed to added experience in conducting the hydrolysis, much of it to a revised procedure of adding the copper sulfate catalyst as a solution instead of as a solid. Summary: The following facts dealing with the hydrolysis of Pontachrome Savin A Base to Pontachrome Flavine A, 125$ have been estab lished: (l) No changes in process between the Tentative Serai-Works Process and the present Dye Works Process have been such as to reduce the yield. --- -2- DUP050040726 (2) No difference has been found among iron, copper, and nickel bombs which appear to influence the yield except that smooth-surfaced copper-lined bombs and smooth-surfaced nickel bombs appear to give good hydrolysis yields almost from the first charge whereas it takes several charges at times to bring the yield from an iron bomb up to its maximum, (3) No essential difference has been found between the plant procedure of neutralizing with sulfuric acid and salting out the dye with sodium sulfate and the obvious method of neutralizing with hydrochloric acid and salting out with salt. The use of the latter procedure appears to give a stronger crude but no better yield. (4) Additives such as ferric oxide, sodium sulfite, "Sitol" (a textile processing agent), pyridine and alcohol have no effect on the hydrolysis. (5) Lead even in small amounts reduces the yield. In large amounts it acts apparently as a reducing agent in stoichiometric relations, (6) Agitation during the hydrolysis is essential. No effort was made to correlate the rate of agitation with the yield. (7) Poly TFE (a plastic) could be used as gasket material without changing in any way the quality or the yield of the dye. (8) The TiCl3 value of standard Pontachrome Flavine A, 125$ does not agree with the nitrogen content by the Kjeldahl method. For the pure free-acid, salt-free product the TiCl3 value is the same a3 the Kjeldahl value. (9) The determination of yield data by means of the in crease of inorganic chlorides content of the hydrolysis mixture is unreliable. . (10) Under any conditions of isolation found in which good dye is obtained there is a filtrate loss of 7.5-8,5$. The dye left in the filtrate la not Pontachrome Flavine A but is either unhydrolyzed base or monodecarboxylated material, both of which have tinctorial strength approximately half that of Pontachrome Flavine A, both of,which are red and dull versus Pontachrome Flavine A. -3- DUP050040727 (11) No catalyst other than copper or a copper salt has been found to be as effective as copper in catalyzing the hydrolysis, (12) Pontachrome Flavine A is stable under the conditions of hydrolysis and undergoes no decarboxylation. (13) Chloro-amino-benzoic acid prepared by the route : ortho . dichlorobenzene ortho-chloro-benzonitrile ortho-chlorobenzoic acid -> 5-nitro-2-chloro-benzoic acid -> 5- amino - 2 - chi oro benzoic acid gives yields of Pontachrome Flavine A at least as good as standard Dye Works material. Experimental Part Most of the results of this investigation may be summarized by tables which are numbered below to correspond with the numbered statements of the summary. So many variables might have been checked on that it was decided to hold all volumes, charge sizes, temperatures, and times of hydrolysis constant after the first one or two series had been run until other factors had been checked, A typical hydrolysis is given below, Typical Hydrolysis: A bomb was loaded with ,0327 moles Pontachrome Flavine A Base, 30,3 cc. 10 N NaOH, O.238 g. CuSO^HsO, and 40,0 cc, water. In charging the bomb the Pontachrome Flavine A Base was mixed with the caustic, the copper sulfate dissolved in the water, and the two mixtures mixed thoroughly either in the bomb or in a beaker. (When our 1-liter autoclave, EX. 46, was charged the amounts were multiplied by 6 for convenience. When our 2-liter autoclave, Ex. 10, was charged the amounts were multiplied by 12.) The charge was heated with rotation for 8 hours at 154-156C, after which time the contents of the bomb were removed with the help of as little hot water as possible, filtered to remove the copper sludge, and the volume of the combined filtrate and washings adjusted to 192 cc. to correspond to the volume of the Dye Works recipe. The temperature of the filtrate was then ad justed to 40 and acid (10 N HC1 or 20 N HgS04) added till the solution was faintly alkaline to Brilliant Yellow paper. After the first series was completed a pH meter was used during the neutralization and "faintly alkaline" was defined as having a pH of 6.8-7.2. After neutralization there was added 10$ salt by volume, the precipitated dye was stirred at 4o'C. for thirty minutes and filtered. Part of the filtrate was used to remove 4- - DUP050040728 the last portions of the dye from the beaker. When the presscake had become.fairly dry It was removed from the filter and dried at 70C. When dry the entire crude sample after being weighed was pulverized as completely as possible in a large glass mortar and dyetested for shade and strength or sent for analysis. Any variations from this typical run, which was designed to duplicate the plant recipe in miniature, will be noted in connection with the tables in which those variations occur. TABLE X Comparison of Process Yields Tentative Semi-Works Process Run (Theory) 1 85.0 2 71.0 3 91,5 4 5 6 7 8 9 Av, 89.2 Tentative Dye Works Process % (Theory) 92.5 91.0 91.7 Modified Dye Works Process (Recipe dated 2/18/42) %.' (Theory) 70.9 76.0 99.0 81.2. 106.0 81.6 105.0 115.0 89.0 91.52 TABLE II Yields From Different Types of Bombs Bun Iron (D 12) % 1 2 5 4 5 6 7 8 9 10 Average 71.0 106.0 87.8 97.0 85.0 86.1 92.5 79.0 100.0 92.1 89.65 Copper Line (B 51) % 92.4 92.4 91.2 98.2 89.1 85.6 Nickel (B 47) % 80.0 102.5 79.8 91.5 -5- 87.4 DUP050040729 TABBE III Comparison of Isolation Methods: (a) neutralization with Sulfuric Acid and Salting with Sodium Sulfate vs, (b) neutralization with Hydrochloric Acid and Salting with Sodium Chloride (10$)_________ No, 1 2 Method A A Dry Weight 36.9 g. Strength 11:10 31.8 97.5 :100 Std.Wt. 33.5 32.6 8- Shade T. N. T. Grn. Grn. T.Brfc. T.N, Brt. 3 A 32.5 95 ;100 34.3 N. Grn. T. Brt. 45 AA 34.1 38.4 102.5 121 slOO :100 33.3 31.7 T. Brt. T. Grn. T. Brt. 6 B 28.9 97.5 :100 29.2 Close 7 B 28.5 88 :100 32.4 T.N. Red T.N. Brt. 8 B 31.7 90 :100 35.2 T. Red T.N, Brt, 9 B 28.3 88 ;100 32.1 T. Grn. T.N. Brt. 10 B 32.0 86 :100 37.2 T. Grn, T.N. Brt. Note; The above runs are aliquot parts of plant charge 221 which was obtained from the plant at the end of the hydrolysis, The material was filtered at 80C . and divided into 10 equal portions:. The average amount of standardized dye from each method is; Method A : 33.08 g. Method B ; 33-20 g. Abbreviations; Std, Wt. = standard weight; T. = trace; N. = noticeably; Grn. = green;'Brt. = bright. 6- - DUP050040730 Jackson Laboratory Notebook 3831-90-1 -90-2 -90-3 -90-4 -90-5 -90-6 -90-7 -90-8 -97-1 -97-2 -97-3 -97-4 -97-5 -97-6 -97-7 175-0 175-E TABLE IV Effect of Additives Additive 1 g. Na2S03 None 1 g. NaaSOa None 0.5 g. Sitol Bomb No., B50 851 D15 B26 B52 None 0.5 g. Sitol None None P3 D13 Al4 850 1 g. Pea03 5 cc. Alcohol 1 g. Fe203 Al4 D13 B51 1 g. EtSH F3 ' None No CUSO4 added_ 813 1 g. Ethyl Mercaptan 852 5 co. Pyridine 852 5 cc. Pyridine B30 0.5 g. PL (leadL Type Bomb Copper l^ned Iron Iron Copper lined Iron Iron Iron Copper lined Iron Iron . Copper lined Iron Iron Copper lined t! Iron Per cent 91.2 89.1 86.3 100.0 100.0 93.7 85.0 99.6 80.3 85.1 86.1 85.6 9.0 82.5 34.0 85.0 68.0 7- - DUP050040731 TABLE V Effect of Lead JLNB Run Autoclave (Iron) % Yield 5831- 91 .94 98 163 106 108 1 2 3 4 5 6 Ex. 46 (1-liter) It n 11 ti 112 7 11 99.2 99.0 87.2 81.7 85.0 81.3 84.0 113 8 " 3essttm25.C 115 9 II8 10 122 11 ti 11 It 89.2 98.5 100.0 125 12 130 13 ti ti 29.8 19.2 3831- 92 93 99 102 105 107 111 114 116 119 123 126 129 132 136 139 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 Ex. 10 (2-liters) 11 ii 11 11 n II ti 11 11 : it 11 it If it 34.2 37.2 82.3 87.9 88.5 82.2 77.2 75.5 89,2 82.6 88.0 88.0 84.8 91.3 93.6 95.0 Remarks Asbestos gasket 11 11 Pb. gasket tl , 11 I! 11 plus 50 g, sheet lead Asbestos gasket 11 11 30 g, Pb added 30 g. Pb added Pb gasket 1! Asbestos gasket 111 .1! 11 11 n 11 in 11 * *' ti 11 11 it 11 11 11 11 it it 11 11 it 11 11 $1 *At tills point it was discovered that a pipe leading from the autoclave contained, a lead gasket about 12-15 inches from top of the autoclave. This was replaced with an asbestos one and the pipes washed out with hot 16$ NaOH. 8- - DUP050040732 TABLE V-A Effect of Lead Compounds! JLNB Bomb 3831-101-1 B50 101-2 , B51 101-3 B52 101-4 P3, 101-5 D15 101-6 Al4 101-7 B13 101-8 A20 Type Bomb Cu. lined 11 n Iron it it it ii Pb. Compound % Yield None 92.6 Pb. shot lessthan20$ Pb. acetate 88,8 PbO 70.0 Granular lead less20$ than None 84.0 FbCOa 92.0/ Pb. acetate 50.5 TABLE VI Effect of Agitation JLNB 3831-110-2 110-3 13 4-A Bomb No B$2 B51 B26 154-B 134-C . 104-1 B47 ' A20 B50 104-5 Al4 104-6 B30 Glass lined None Glass lined None Iron Normal JNo catalyst. Nickel Normal Iron None Copper lined Normal 1 No catalys-y Iron r- Normal -1 [jfo catalysy Iron [Normal -1 No catalyst] 51.0 63.5 102.5 68.5 86.6 76.0 55.1 TABLE VII Effect of Poly TPE JLNB 3831-170 383I-I72 Bomb B52 tt Type Bomb Cu, lined * " % Yield 75.0 90.0 *The previous history of this bomb could not be determined. Both runs were normal runs with a 5.5 g, triangle of sheet Poly TPE inserted into the bomb before hydrolysis. 9- - DUP050040733 TABLE VIII Analyses of Pontachrome Flavine A JLNB 5831-147 165-3 165 171 168 % Purity by Material F (Kjeldahl TiCla Free Acid 96.0" 97.2 Standard, Lot 1 53.0 47.0 Standard, Lot 1 530 47.2 Free Acid 96.9 Free Acid 97.5 Acid No. "93TB 96.7 98.2 The free acid of Pontachrome Flavine A was prepared by dissolving 100 g. of Pontachrome Flo.vine A 125$ in a liter of boiling water, adding HG1 till the solution is strongly acid to Congo Red paper, filtering and washing with 5 200-ml. portions of hot water. 40.85 G. of the free acid 100$ was obtained from a calculated amount of 41.02 g. based on a TiCl3 determination of the standard product. TABLE IX Relation of Hydrolysis to Increase in Inorganic Chlorides by Analyses JLNB -125 126 136 144 144 162-A 162-B 162-0 162-D % Chlorides Type Run at start at end Pb present Formal Formal Aliquot from chg. 280 Recheck " Formal charge 6 hr. run Formal charge 4 hrJ run Normal charge 3 hr. run Formal charge 1 hr. run 3.09 3.16 3.18 6.46 6.31 0.15 0.15 0.40 0.19 3.28 4.02 4.20 6.54 6.62 0.21 0.13 0.74 0.65 Hydrolysis calculated by dyetest $ 18.1 91.6 109.0 145 $ 29.8- 88.0 93.6 85.4 171 6.34 85.4- Negative 35.8 39.6 -10- DUP050040734  JLNB 3831-102-AB 102-CD 103-AB 103-CD TABLE X Dye in Filtrates A Dye Isolated Type Run \ by TiCl3 % Neutralized with HOI. Add NaCl ' (salt). 70.7 Neutralized with Ha304. Add NaaS04 (sodium sulfate). 82.4 Neutralized with H2SO4. Added NaaS04. 84.4 Neutralized with HOI. Added NaCI. 82.4 B Dye in Filtrate by TiCle $ 8.65 8.51 7.5 7.2 * Yield *by Dyetest of a % 85.0 85.3 86.3 37.8 Note: The constitution of the dye remaining in the filtrate was not determined. It is not Pontachrome Flavine A, hut gives very weak, dull, red dyeings. Its tinctorial strength is approxi mately that of unhydrolyzed "base or half that of Pontachrome Flavine A. 1 1- . - DUP050040735 , TABU! XI P O I <5 P KN o KN O KN KN o p 1 m O O o o in o Q in o VO vcou ckon H KN H P O KN JOo K S ?2 rH o KN 0 & J5 CM KN KN O <O OS o 00 CO CM KN in 'HKNI KN H UN St CM KN kn o st CM o o in o H CM ON VO CO 500 A t3 KON |of> |cTm\ 3L K Q P6 o in <P ft id _ *> KN KN CM (d <? O KN O ! W A O IP . . *4 fiE ' <c o p 5w o co ON N- 00 *v CM VO rH H in in O rH k \ Jt in K- KN co rH rH tv r~H VO KN CM O o KN o 3 05 KN KN * O O o s in O VO |v t- H Om H ON m J* CM KN tv CM * JIN<* H O KN 0 0 * 3 O0 O O tv .KN O J* rH VO in rH co oo o On On in h- P P H G* Op t* <H *"* A *p0 oo soi U -H W o, G O G H KN CM s* O KN s3 KN O o PC to O 0 H 2 a KN rH ON rH H co o ON On m H P p S 4* 4) KN K\ t- P O CM Pi KN KN | in o <D o t- rH . om in o in st UN H 00 in in rH m tv P G OAh t*-- KN <M O KN O K\ O O tv KN CM c m VO O KN rH CM KN O9 O m 0 o to mp o m 4* & &R H *) B r-< r-| 4J 5 O vo o H ON UN st <n KN , M P to P u 13 O UN t" 0H in o in rH m N- G P +J PG kn VOk n UN CO to .to 4 >* H P *> | a a r-i 4> P *0 * & **- rH f >5i - g .. O P s 1fa *> O fa U t j r> JE to >R p a P A N * DUP050040736 TABLE XII Effect of Hydrolysis Conditions on ______Pontachrome Flavine A JLNB-3831-140,149 Run 1 2 3 4 5 Bomb B-26 A-14 Ex-10 Ex-10 Ex-10* Mola dye Mols NaOH Wt.CuSOj, g. Wt.HgO g. Isolation pH Crude Wt. Strength Mol Return, g. $ Return Shade .0327 0.303 0.37 4 0.0 6.8-7.2 19.5 8:10 730 98.6 Close .0327 0.303 0.37 40.0 6.8-7.2 I?.? 80:95 643 87.0 Close .0327 0.303 .0327 0,305 , 0654 O.606 0.37 0.37 0,74 56,6 56.6 II3.2 appx.7.0 appx.7*01 appx.7.0 23.1 21.5 53.3 75:85 75:80 ' 1:1 753 101.0 703 95.0 815 110$ Close Close T.red T.green T.green T.bright Buna 3* 4, 5 are aliquot parts isolated from an autoclave run. Samples from this run were analyzed for azo nitrogen by TiCl, and for C0p 'before heating and for the same after heating 8 hours. The data for this determination follow: Charge to Autoclave Ex, 10; Pontachrome Flavine A, 125$ (.0392 moles) NaOH (30$ solution) Water Copper Sulfate Total Sample "An for analysis To Autoclave (0.3675 mole) After Hydrolysis: I Water to Wash Autoclave Total Recovered Charge Sample "BMfor Analysis Left ;for isolation (.3482 mol) 1.0 mol 5215 g solution 0.0327 mol = 171 g. solution g. 291.0 510.0 680.0 4.44 1485.44 93.00 1392.44 527.00 1920.00 100.0 1820.0 -13- DUP050040737 Analyses; "A" 0.10# carbon dioxide "B" 0.15# carbon dioxide Difference 0.05# carbon dioxide Increase 0.696 g. carbon dioxide = ,0158 mol - 4 .3# mono-decarboxylation assuming carbon dioxide to have come from the Pontachrome Flavine A itself. Since the average amount of dye recovered from the hydrolysis was by dyetest 98.3$ and since there appears to be a tendency for the recovered dye to be green and bright versus the starting material; the slight increase in the amount of carbon dioxide appears to have questionable significance. TABLE XIII Comparison of Samples of Amino-chloro-benzoic (JLNB-4053-26.32) Coupling, # yield (By TiCl^) Plant Charge 4 91.5 (4 runs) 3898-98-A 96.1 (2 runs) 3898-103A 92,8 (2 runs) Hydrolysis yield, # 93.8 (4 runs) 87.4 (2 runs) 88.2 (2 runs) Overall yield, # 85,8 (4 runs) 84.0 (2 runs) 82.0 (2 runs) Note; Both samples 3898-98-A, 103-A formed colorless diazo solutions. Each time the diazo solution from Plant Charge 4 was highly colored. Submitted for typing - October 21, 1943 Typed - November 24, 1943 Marjorie N. Reign -14V' .fn f?4 DUP050040738