Document ovX8q0mN4j8nM2J612e1naZR

VOLUME I1 New York D . VAN NOSTRAND COMPANY, INC. 250 Fourth Avenue 1945 4/37 COPYRIGH1T9,45 BY -D. VAN NOSTRAND COMPANY,INC. All Rights Resewed This book, 01 any parts thereof, may not be reproduced in any form without unitten Permission from the author and the psblirhers. PRINTED I N T H E UNITED STATES OF AMERICA THE WILSONIABANCKGROUND 11 technical or commercial problems, so that fair and equitable rates might be determined.` T h e logic of Howard's quiet-spoken arguments appealed to several members of the Committee, but time pressed. No congressman wanted to become involved in the highly technical details of a scientifically drawn chemical schedule. Such a tariff would be obviously to the advantage of the manufacturers. Their official offer of cooperation was made in good faith, but it was naturally suspect. After the President's spirited attack upon the representatives of all trade and industrial organizations, it was quite impossible for the Democratic majority of the Committee to agree to any such proposal. Witness after witness cited specific instances of chemical raw materials, previously on the free list, that were now being made dutiable, while at the same time Iower rates were being proposed on finished products made from identical raw materials. It was proposed, for example, to take from the free list all the coal-tar raw materials in Paragraphs 23 and 24 and place a duty of S per cent on the former and 10 per cent on the Iatter section.8 A joint statement signed by Edward Mallinckrodt, Jr,, A. G. Rosengarten, John F. Queeny, John Anderson, Donald McKesson, Otto Schaefer, and E. W. Preston,O pointed out that, thanks to domestic competition, vanillin, which formerly sold for $5 an ounce, was now selling for 354. The current duty of 20d had already been reduced from SO# in the Payne Tariff. The proposed bill cut the vanillin duty to IO&, but at the same time removed from the free list three of its important raw materials: cloves dutiable at 2$ a pound; caustic potash, %&; and benzene, S&. In other words, the rate on the finished organic chemical was to be cut 50 per c p t , but of the duties on six chief raw materials it was proposed to take three off the free list and raise the duty on two others.'O Summarizing, Henry Howard analyzed the changes proposed on 300 specific chemical items of which 97 (roughly a third) were raw materials and the rest finished products. Of the 97 raw materials, 80 were free under the Payne Act of 1909 and duties were increased on prac- tically all the 17 others. The revenue from the finished chemicals under the Act of 1909 had been $1,826,955, while the estimated revenue from their raw materials under the proposed rates would be $6,081,060, an increase of approximately $4,000,000.11As the brief of Merck & Company concluded: "Your Honorable Chairman is reported to have stated: `To reach this result I prefer to lower the tariff by taking bricks off the top of the wall rather than by dynamiting the structure from the bottom.' W e would respectfully express our conviction that the as=ssment of duty on such raw materials now being supplied to manu- TARIFF DEPRESSION TO WAR BOOM 17 sixbe exact, the New York Stock Exchange reopened. Within another months confidence had so returned that shrewd bargain hunters began accumulating high-grade securities whose prices had been forced to an abnormal low, due to the unloading on this market of American shares previously held abroad. In view of this flood of foreign-owned securities which we had to absorb, the stock market debacle is quite understandable. It is not SO easy to comprehend, however, why the sudden outbreak of war should have sent chemical prices spinning downwards. Seemingly little per- spicacity should be needed to anticipate the enormous demands that a big European war would make upon American chemical supplies. True, at that time, not even the German High Command appreciated the vast amounts of benzene and toluene, of ammonia, of sulfuric and nitric acids, of caustic soda and soda ash, of chlorine and bromine needed in modem, large-scale warfare. While the Kaiser's armies were marching through Belgium, no one in this country dreamed that American chemical plants would be called upon not only to munition the Allies, but also in a great measure to furnish the neutral world with chemicals formerly bought from Great Britain and Germany. Even if the extent and length of the war were quite unsuspected and its chemical demands woefully underestimated, we had plenty of precedents, and good reason, too, to remember that war requires ammunition and medical supplies, which greatly increase chemical consumption. American chemical manufacturers knew these facts, but they could not then see why the older, well-organized, diversified chemical industries Pof England and Germany, both producing an ex ortable surplus of many chemicals, should not be able to take care o all their own war requirerifents. Our chemical industrialists had reason to be concerned about the domestic situation and they spent many a sleepless night during that hot, muggy August of 1914, speculating upon the course of the war and the future of American chemical business. Each morning they found their desks piled high with postponements and cancellations of shipping instructions from their regular contract customers. As deliveries slowed down and inventories began to pile up, their nervousness grew. Not all of them had the patience and courage to reply as Edward Mallinckrodt, Sr., did. When his youthful assistant, Fred Russe, urged that since there was sufficient stock for several months, they should close the plant and keep only a skeleton force a t work, Mallinckrodt said: "Things are pretty bad in St. Louis, and if we discharge several hundred of our people, that would cause a good deal of hardship, even suffering in some cases; but if we keep them all at work, I am the only one who is hurt. Remember, too, that just as we don't have good times all the time, so we won't have bad times forever. Be- of coal, none by synthesis; but we were recovering more than 10,000,- 000 gallons of benzene a year, sufficient for our needs for it as a fuel, solvent, and dry-cleaning agent." Naturally, the first call from the Allies to us for high-explosive materials was for benzene. Following the same logic, the conversion of benzene to phenol by sulfonation was the first large-scale, aromatic organic synthesis we attempted. As this involves a rather simple technique, the phenol synthesis was a good introductory experience for both our chemists and our plant operators. Furthermore, the commercial incentives to produce phenol were tempting. During the early months of 1914 the German Dye Trust, possibly with foreknowledge of the coming war,# had been raiding the world's phenol market, challenging England's last coal-tar stronghold. The price of phenol in New York had dropped to 7C a pound, which at the time was said to be less than the cost of production.'' By January 1915, the price was SOB, a month later it jumped to $1.00, and by July had reached $1.50.'' The cost of benzene had, of course, advanced at the same time, but not so rapid1y.t The prospective profits stimulated, as we shall see, a number of hardy chemical adventurers to undertake this untried operation. From the synthesis of phenol to its conversion into picric acid was a logical step, since picric acid was eagerly sought by English and French armies both, and afforded opportunity for an additional profit. 1 Phenol to picric acid was accomplished by sulfonation, followed by nitration of the disulfonic acid. Neither operation was particularly dficult, but each step required a large excess of exceedingly pure, high-strength acid, which at that time was not available in this country in the quantities required. On the heels of thearitish demands for benzene and phenol came a call for toluene and aniline. Thus the American coaltar industry was launched on a great wave of munition demand. Thus, too, as this new venture advanced, it created a demand for more and more coal-tar crudes and intermediates and for new grades and undreamed-of quantities of many inorganic chemicals. *"I do not believe the German Dye Trust had any foreknowledge of the coming war. M y reason is that I spent a few days in the Leverkusen works of the Bayer Company in May 1914, and made a contract for the Merrimac Company to act as agent of the Bayer Company for the steam meters which they were usmg throughout their works at that time, which had impressed me most favorably. I made this contract directly with Dr. Carl Duisberg. It was not an important matter, but he gave considerable time to it, which he certainly would not have done, if he had been forewarned of the coming war. T h e first shipment of these steam meters arrived in N e w York about a week after the war started." (Henry Howard, to author, Sepc. 21, 1942.) t Benzene quotations, spot N. Y., were: July 1914, 206 Ib.; Jan. 1915, 346; Feb. 1915, 356; July 1915, 754. See also Appendix 11. f Picric acid quotations, in kegs, f.o.b., were: July 1914, 406 lb.; Jan. 1915, $1.00;Feb. 1915, $1.25; July 1915, $1.50. See also Appendix 11. XIALLY FORL SPUR U. S. ?D FOR COAL- merican symul," it is the zl profligacy. ,ave ridiculed retically, it is where it was . erected anybr, easily shut is of the vast itain of metal id gauges, re;teady market teering metali coking coal )w-cost ovens market or the :losed or even : to make the 1 'as emphasized 1 are the eco)oth the Pitts; with natural ,-priced. Our Benzol was a ;ven when the 1 so to enrich coverable-this was before the synthesis of phenol from benzene-was commercially insignhcant. The two remaining crudes, naphthalene and anthracene, were recovered from the creosote-oil fractions, but at that time crude naphthalene was imported and refined here, while the market for anthracene was very small. Furthermore, creosote oil found ready sale as a wood preservative-in fact, American consumption was twice greater than production-so that in view of the limited call for these crudes, their extraction was not commercially tern~ting.~Tar-distilling practice then also produced about 70 per cent of its tar as pitch. While Pin Euro e coal tar found use only as fuel, here it had a profitable market or roofing, waterproofing, and increasingly for road building. At this stage of our chemical development, all these crude coal-tar products were largely supplied by tar refiners operating on low-cost by-product tar from the gas work^.^ Thus the coke plant at gasworks was producing but one chemical, ammonia, which did not have to meet this competition. Either as crude liquor or converted to sulfate, ammonia recovery was a sound, commonly profitable chemical enterprise, but this single product did not justify a by-product coke in- dustry." So little financial incentive was there to produce coke by-products, that the first recovery ovens in the United States were an adjunct to a Solvay soda-ammonia alkali plant. In 1893, at its Syracuse plant, the Solvay Process Company built 12 Semet-Solvay ovens developed by its associate company in Belgium. The avowed purpose was to produce raw materials for its own use: ammonia for reaction with brine; coke to bum with limestone; fuel gas to make steam for the ammonia- chloride stills. Six years later, in June 1899, the New England Coal & Coke Company installed 400 Otto-Hoffmann ovens, at Everett, Massa- chusetts, primarily to produce illuminating gas. t Three years later, * Coke-oven ammonia and ammonium sulfate production, 1912-22, compared with OFproduction from other sources, is shown in A pendix XXI. t "This is not quite accurate. A number years before, Henry M. Whimey of Boston obtained control of the Dominion Coal Co. in Nova Scotia. His idea had been t o supply the New England market, but the coal turned out to be a poor qudity almost impossible to burn in plants built for burning high-grade N e w River coal. TO . . .save his investment and find a market for his coal, he built the coke ovens referred to. T h e gas sold to the Boston Consolidated Co. for use in Boston and suburbs and the coke for household use in competition with anthracite. Later I persuaded this company to erect a small blast furnace for the production of foundry iron, which made a market for Merrimac's pyrites cinder. Early in 1915 I also persuaded the coke,works to put in a l i g h t 4 plant to save the benzene, toluene, and xylene. This light oil was shipped to Woburn where we refined it in the N e w England Mfg. Co. and turned the benzene into phenol and picric acid. W e built a TNT plant under the design and supervision of Oscar Gumnann & Sons of London, but it blew up before it got into full operation. After this we contented ourselves in selling the pure toluene at a very high price." (Henry Howard, to author, Aug. 23, 1943.) THE BY-PRODUCTS FROM COAL 127 tant cities as Boston, Indianapolis, Baltimore, and Milwaukee coming from these sources.8 Almost without exception the retort-oven op- erators recovered their ammonia, and because of the growing demand for ammonium sulfate in fertilizers, an increasing quantity was converted to this material. Recovery of the chemical by-products from coal tar was neglected for lack of a market.' The total value of coal-tar crudes produced in 1914-mostly benzene-amounted to only $997,000.' At the end of 1913, sixteen plants were producing so-called light oil,t most of which went toward enriching illuminating gas.'O Several of these were oper- ated by the Semet-Solvay Company which made a practice of recover- kig crude benzene at all its coking operations and regularly using it to step up the quality of illuminating gas." Pure benzene and toluene were distilled from crude light oil in two or three small plants, the principal one being operated by the Barrett Manufacturing Company. 1 Refined naphthalene was produced in two plants and used exclusively as a moth preventive. There was but a single producer of phenol, Barretr, and no refiner of anthracene.l* Much of the coal tar produced was separated only into cresote oil and pitch, which were sold for wood preserving, road building, or roofing. Tentative starts towards a production of pure coal-tar products had been attempted. Synthetic phenol from benzene had been produced as early as 1900 by the Semet-Solvay Company at Syracuse. For several years an output that reached a peak of 2,500 p o u d s daily had been For coal-tar crudes production figures, 1915-22, see Appendix XXII. t `'More correctly, `ps-benzol,' which closely approximates what the Europeans describe as `light oil.' Light oil as such was never recovered in this counuy. It was the first fraction from the distillation of coal tar, but if you get out the gas-benzol in the fim place, it never gets into the tar, therefore our ,mcarry no light-oil fraction." (J. R. M. Klocz, to author, Jan. 29, 1943.) $ "The source of this information seems to have been F. E. Dodge, who was at one time supt. of the Frankford Refinery of the Barrett Mfg. Co.and later worked for me putting in benzol-recovery plants at several steel companies with by-product coke ovens. I chink he is a lirtle mixed up. Banett had one principal plant at Frankford which operated regularly on gas-benzol and such light oil as they could get and con- . . .siderable gas drips and Pintsch hydrocarbon. T h e y made nitration grade of ben- zene, 90% benzol, and a small amount of pure toluene. T h e United Gas Improve- ment plant at Philadelphia, under the late Paul Thompson, was monkeying with E`Oduction of a few primaries including benzene and naphthalene. Barrea was ma mg considerable phenol and I don't think the primary products industry was in quite so embryonic a state as you point out. I came into the industry in 1909, and at that time, Dr. Harry W. Jayne (manager of Barrett Chemical Dept. at Frankford, later Jayne & Chase before being absorbed by the M. Eheret, Jr., CO.) was considered by the Eng- lish and Germans to be one of the five world authorities in coal-tar chemistry. H e was the father of D. W. Jayne of du Pont, whose assistant I was for many years. If Some of the capitalists and bankers who later crept in on this industry would have listened to Dr. Harry Jayne, the industry would have been way ahead of where it was in 1915." (1.R. M. Klotz, to author, Jan. 29, 1943.) 128 CRITICAL Raw MATERIALS synthesized to picric acid and sold to the United States Army for muniRather optimistically anticipating an American demand for coal-tar chemicals, this company in 1920 joined with Barrett and General Chemical in forming the Benzol Products Company. It was a logical alliance. Solvay produced the raw material from its coke ovens. Barrett had considerable experience with refining operations and apparatus, having at the time a small plant making aniline oil and toluidine. General Chemical was included as a producer of sulfuric and nitric acids, large quantities of which were required in the proposed operations. The Benzol Products Company took over the old nitration plant of Barrett at Frankford. This was rebuilt by an Englishman named A. B. Mitchell, son of the principal partner of W. G. Barnes & Com- pany, chemical merchants in London representing Cassella and others that later went into the I. G. Farbenindustrie. Mitchell entirely rebuilt the plant, and with technicians supplied by General Chemical and Barrett, revamped the processes. Aniline oil and nitrobenzene were manufactured,14 and by the time%e war broke out, Benzol Products had demonstrated it could produce high-quality products economically." Our pitifully small demand for coal-tar crudes was evidenced by total imports of less than a million-dollars value annually. Coal-tar crudes had entered duty-free until the Underwood Tariff (1913), when "for revenue only," the Democratic Congress placed an ad valorem duty of 5 per cent on benzene, toluene, xylene, naphthalene, with phenol, anthracene, and cresol still on the free list. But the true state of our coal-tar chemical industry was revealed in the cold figures of our imports of the derivatives-dyes, aromatics, medicines-which annually totaled over $10,000,000 in value.15 It has been estimated the value of these coal-tar products doubled and sometimes trebled by the time they reached American consumers. Then came the European war and the picture changed as if a hurri- cane had swept across the landscape. The neglected coal-tar products were suddenly in clamorous demand. Benzene for synthesis into phenol to be converted into picric acid, and toluene to be nitrated to TNT, were prime munitions for the British, French, and Russians. Naphtha- lene and anthracene were "must materials'' in our frantic efforts to establish a coal-tar chemical industry. The nice steady call for sulfate "If I can modestly say so, we put the fear of God into the Germans as we actually made both nitrobenzene and aniline oil. The Swiss chemical companies, to whom we offered to export these, immediately put out samples in their laboratory as standards which the German suppliers (Badische) had to agree to meet in quality or the Swiss would buy from us. This, of course, was lese majesty to the Germans as they liked to give the impression to the world that they were the only quality makers of anything. Their retort to our quality was to im rove their own and cut the price about 2# per pound." (J. R. M. Klotz, to author, Pan. 29, 1943.) I I I t -i i i THE BY-PRODUCTS FROM COAL 129 of ammonia became a panicky appeal for help from fertilizer and munitions makers. T h e first impact of the war stunned our coke producers and tar refiners. They fumbled about, uncertain whether to expand or to wait the coming peace. The steel companies were the first to recover. With a flourish Carnegie and Maryland announced l6 new by-product plants. This was only the speeding up of an expansion undertaken before the war, but by the turn of the year, most leading steel producers- notably United States Steel, Lackawanna, Maryland, and Republic "- were rushing installation of equipment to recover light oils from which to separate benzene and toluene. Under the impetus of the war, there was a great demand for new ovens and by-product recovery plants, so that between 1915 and 1921 nearly 4,000 coke ovens of the Koppers type alone, were built. At the same time the vertical-flued oven was introduced in the gas industry, plants being built at Kearny and Camden, New Jersey, St. Louis, St. Paul, and Providence. During this six- year period the output of by-product cake increased nearly sixteen million tons per year?* Munitions orders were flooding the country, sweeping the price of benzene from 40$ to $1.25 a gallon; toluene to $4.00 a gallon; phenol to $1.20 a pound; naphthalene from 2%$ to lot a p 0 ~ n d . l ~These fabulous prices touched off the wildest explosion of chemical activity this country had ever seen." The combination of greater output and fancy prices shoved up the value of coal-tar crudes from $997,000 in 1914 to $7,340,000 in 1915. These astonishing figures were to be capped in 1916 by a value greater than $30,000,000.21 This last figure indicated real progress for, during 1916, expanded supply began to catch up somewhat with the exorbitant demand, and prices began definitely to decline. By the end of that year benzene was selling for 60$ a gallon, pure toluene for $2.50 a gallon, and phenol for 65t a pound." During 1915 fifteen more plants, making a total of thirty, were equipped with benzol-recovery apparatus and that year over 16,600,000 gallons of benzol products were ma~keted.'~Only a third of the recov- ery plants had the opportunity or time to wring two gallons of light oil from a ton of coal: * several secured less than a gallon?* The new * "This, I believe, is misleading. All the by-product plants built after the beginning of the war were of the finest type of construction. I believe most of them are still in operation with much of the original equipment. I recollect that a t least one of the plants I visired at that time had white d e walls in the distilling room. While they were built in record time, they were thoroughly modem at that time. With re ard to yield, I think you have misinterpreted the paragraph in Minerd Resprrrces, tKe fact being that one reason for the relatively low yield of 1.54 gal. per ton of coal, which js stated in that reference as against the ultimate anticipation of 2% gal., resulted largely from the fact that all of the gas was not fully stripped of these aromatic hydroc h o n s . It was only later that gas requirements for public utilities were changed, 130 CRITICAL h w MATERIALS by-product coke plant a t Farrell, Pennsylvania, so cheerfully announced by the Carnegie Steel Company just after the war broke out, was an unusual example of unexpected dficulties. The contract had been let to Carl Still i?c Company, and when these good Germans realized that the benzene and toluene to be produced would make ammunition for the Allies, they instituted a studied campaign of sabotage till in the end, to get the plant finished and operating at all, the steel company had to dismiss the contractors and finish the job itself.25 b I I` * In the early stages the greatest demands were from the British and French Governments for phenol, toluene, and refined naphthalene. 1I : Exorbitant prices promoted extraordinary effo m to increase the supply of benzene to be synthesized to phenol, and to work up other sources f of toluene. Prior to the war we had imported phenol for medicines, disinfectants, tI and the new plastics. Accordingly, when England placed an embargo on this essential material, we were unable to supply even our modest peacetime needs, to say nothing of the new war demands." Barrett moved quickly to increase Since the phenol content of tar is but 0.7 per cent and practice was then recovering only about 0.25 per cent, natural phenol supplies were plainly inadequate and recourse must be had to synthetic phenol from the familiar sulfonation of benzene. One of the first to suffer from the dearth of phenol was Thomas A. Edison. H e needed large supplies for his phonograph records and with characteristic energy he adopted the benzene synthesis. By the fall of 1914 he was furnishing his own needs. This meritorious accomplish- ment was exploited for much more than it was worth by the daily press, for chemicals had become news and Edison was a name with which to conjure. So the great inventor was sharply criticized '`for countenanc- ing this wild publicity and for claiming, a t least by implication, that this well-known process was his own invention, He paid for this super- publicity by becoming innocently involved in what became known as "the phenol scandal." Early in 1915, the newspapers carried the story that Edison had bought the Cambria Steel Company's output of light oil and was build- ing a refining plant at Silver Lake, New Jersey, with a daily capacity of 18,000 gallons of benzene to be converted into phenol."* Here was a sizable supply which a little group of Germans plotted to keep out of Etwhich fact you cite later, and then all the was fully stripped. Experience has led to the much higher recoveries now made, there are factors such as the cycle of coking time whch affects these yields. In the tremendous war pressure, coal is coked at a minimum cycle and this is bound to affect the yields of light oil." (David W. J a p e , to author, Nov. 17, 1942.). For phenol production and mpom, see Appendix XXIII. THE B Y - P R O D UF~RSOM COAL 131 Allied munitions plants. Edison turned the marketing of his surplus over -to the American Oil & Supply Company, well-known chemical jobbers of Newark, New Jersey, and almost the next day they sold it on contract to the "Chemical Exchange association.^' The price was high, and as this buyer was an unknown firm, it put up $100,000 in cash, advance payment. T h e phenol was delivered to the Heyden Chemical Works, American branch of Chemische Fabrik von Heyden. For every pound of phenol received Heyden returned a pound of salicy& acid which Chemical Exchange in turn sold to Bayer Company, American subsidiary of the great German firm which controlled the patents and trade name on aspirin (acetylsalicylic acid).* All this was roundabout, but speculative juggling was rife in the chemical market and nothing on the surface aroused suspicion. Shortly after this deal was completed, Dr. Hugo Schweitzer, chief chemist of Bayer Company, and his good friend, Richard Kny, active head of Kny-Scheerer Company, important manufacturers of surgical instruments, gave a dinner at the Hotel Astor in honor of Dr. Albert, financial advisor of the German Embassy in Washington. It was an hilariously happy celebration. The hosts were the parmers of the dummy company known as the Chemical Exchange Association. They had good reason to be grateful to Dr. Albert, who had not only worked out the devious details of this chemical coup, but had also provided the $100,000 cash. They had good regon to celebrate, too, for their net profit on the deal was $816,000. Also they were converting large quantities of phenol into a harmless medicinal chemical.2s But Edison was not the only producer of phenol. By the middle of 1916, he had many rivals, big and little, producing natural and s p - rhetic material. t Combined, they required an increased production of pure benzene which reached the astonishing total of 21,079,500 gallons in 1916 30 and 40,387,929 gallons in 1917. In the latter year their output of phenol, natural and synthetic, was 64,146,499 Among the many phenol producers of the war period, a couple stand Out. The Schlesinger interests controlling the Milwaukee Coke & Gas Company, under the active managership of John W. Schaeffer, built a phenol plant on a farm they purchased near Carrollville, Wisconsin. See Vol. 111, Chap. 21. f Semet-Solvay Co., Barren Co., Buttenvorth-Judson Corp., Dow Chemical Co.,Aema Evlosit*es Co., Newport Co., New England Mf . Co.. Monsanto Chemical Works, United Gas Improvement Co., National Synthetic Eo., U. S.Standard Chemical Works, British-American Chemical Co.,Bayer Co., Stillwell Chemical Co., Carbolite Chemical G - 7 Pirnburgh Coal Products Co., General coal Products Co., Neidich Process Co., c u t i s & Hardy, and the Middlesex Chemical Co. (See Weekly Dnrg Mktr. 3, June 28, 1916.) i /:it< 1 i i I i t 4 I t I 132 CRITICAL RAW MATERIALS This operation, which was under John R. M. Klotz,1c achieved an output of 135 tons daily. Just before the Armistice, the coke plant was revamped and Koppers ovens installed, while enlargement of the phenol production was planned. Most of the Newport phenol went to J. P. Morgan 8r Company for shipment to the Allies, and the French Purchasing Commission adopted the product of this plant as the standard upon which its specifications were based."a T o incrase &e supply of toluene, various syntheses were attempted. Cymene from spruce turpentine, a waste product of the sulfite paper mills, when treated with anhydrous aluminum chloride in the presence of benzene, according to the well-known Friedel-Crafts reaction, produces toluene and cumol. T h e latter can be oxidized directly to benzoic acid, an additional saving of the toluene commonly used to make this useful acid. Like hundreds of chemical proposals of those days, perfectly feasible on pa er, this project came to nothing for lack of raw materials. The s d t e mills were not interested in recovering the turpentine,s3 and cheap anhydrous aluminum chloride was to come later with its use in petroleum refining and the production of synthetic anthraquinone. Another toluene process enthusiastically publicized in its laboratory stage failed on a commercial scale. In this respect it, too, was typical of many organic chemical projects of the war period. Dr. Walter Rittman of the Bureau of R4ines proposed to pass the vapors of high-boiling Detroleum distillates through metallie tubes at a temperature of 500" duce benzene and toluene?' Approved by govehment officials, a contract was made with the Aema Explosives Company to work the process commercially. After a year's trial, the Company threw up the project. Yields were so scanty that costs were prohibitive, and furthermore, it was impossible to remove traces of paraffin hydrocarbons remined as impurities."" After we became active combatants, the necessity for more coal-tar crudes-es ecially more toluene-was intensified. Fortunately the recovery o f t h e coke by-products had come a 1 Technique had made as great advances as productio;. B> 1918, cokeoven operators turned out 87,562,094 gallons o of which they separated on the spot as benzene, toiuene, solvekt naphtha, and xylene. In addition, there came from the coke ovens that year 16,088,000 pounds of na~hthalene.~"One step farther in coal-tar prod- . i ' * Formerly with Barren and after the war engaged as a consultant, Klotz, who was trained at U. Pa., was later associated with Standard Oil (N. J.) and played an hponant part in the commercial development of petroleum chemicals. ; d an outdant was ne phenol t to J. P. :nch Pur: standard ittempted. lfite paper e presence xion, pro- 3y to ben- :d to make :hose days, ior lack of mering the come later mhetic an- , laboratory was typical Walter Ritthigh-boiling ure of 500" inch to proicials, a conrk the procirew up the and further- ocarbons re- nore coal-tar ately the re- since 1914. r 1918, coke- , 96 per cent solvent naphirens that year coal-tar prod1-101:~most of Klotz, who was id played an in- THE BY-PRODUCTS FROM COAL 133 it immediately nitrated to picric acid. Most of this picric acid was in turn made according to French Government specifications and sold to the United States Government, which delivered it to the French in payment for our heavy purchases of guns and ammunition for the A.E.F."* The measure of this progress was double-checked by the acid test of dollars, for while total output of coal-tar crudes increased some 25 per cent during 1917, total value declined $1,500,000.39 Behind these cold figures were gigantic labors, and now one more , supreme effort was called for. The needs of our Army for TNT, piled on top of British requirements, created in 1917-18 an extra, unbalanced demand for toluene. Our Army and Navy had accumulated no stock of this modern muni- tion, nor arranged any assured supply of its essential ingredient. Even after the declaration of war, a t the first meeting of the General Muni- tions Board, professional representatives of both armed services had listened listlessly to Leland Summers' warnings of an impending short- age of toluene, Within a couple of months, however, they were crying frantically for TNT; sending experts to the recovery plants to squeeze the last drop out of the benzene fractions; begging the gas companies to rob the kitchen stove and parlor lighting jets by stripping this priceless ingredient; * experimenting with new ideas to crack toluene out of petroleum. 8 T o eke out supplies quickly, the best expedient was to strip city gas. Contracts were accordingly made with the utilities in New York and Brooklyn, Boston, New Haven, Albany, Utica, Elizabeth, Washingcon, Detroit, St. Louis, New Orleans, Denver, and Seattle, and the good citizens of these cities unwittingly "did their bit" by getting less heat and light. In New York City, due to the stripping of toluene, the heating value of city gas was reduced 6 per cent and the candle power ]OWered from 22 to 16. Plants to carry out this program began building lare in November 1917, and the first units were in successful operation the following April. Not only did the apparatus have to be made, but a skilled operating staff was trained, a notable accomplishment, well worth the cost of approximately $7,500,000.40At Standard Oil of - Indiana, Thomas Cooke did an outstanding piece of chemical engineer- *"As a marter of fact, the removal of toluene rather improved the light, .for removal of the vapors of these heavy liquids made the gas lighter and less inclined to smoke and clog the burnen. T h e early source of toluene was the condensate or `drip' Pumped from the gas mains. There was quite a volume of this in the days when LW'companies were delivering a gas which would show a high candle power when burned in an open flame burner. T h e toluene and other consutuenrs existed in *e Psas T o n rather than as m e gases, and condensed out as the gas cooled: toh- benzene+ and other constituents were separated by distillation." (John M. Morehead, to author, Feb. 15, 1944.) 136 CRITICAL RAW MATERIALS lapsed like a burst balloon and the most optimistic chemical man could not dream where the enormous surplus capacity might be placed. By- product benzene output had jumped from a prewar 2,516,000 gallons to 43,805,000; toluene from 623,000 gallons to 8,861,000; naphthalene from 196,000 pounds to over 16,000,000.y Recovery plants now ex- ceeded the capacity of the beehive ovens. The cry of insistent demand changed overnight to a wail of oversupply. By-product ammonia was on the same uncomfortable spot. Total production in terms of net tons of sulfate equivalent had been shoved up from 186,749 in 1914 to 378,328 in 1918. These figures include ammonia from gasworks; that only from by-product ovens was 143,249 I in 1914 and 348,654 in 1918.5L The use of sulfate for fertilizer had 1 grown like Jack's beanstalk, but nobody dared hope that normal needs 1 in plant food and for refrigeration could absorb the increased output. i In the wild wartime markets, quotations of sulfate had moved up to $7.80 per 100 pounds in July 1918, when the War Industries Board i i fixed the price at $4.50, or half again higher than prewar. At the same time, anhydrous ammonia prices were set at 30d a pound and aqua ammonia a t QY4#.52 At the request of the Food Administration, Herf If! & Frerichs of St. Louis doubled their capacity for liquid ammonia. Frerichst was asked to duplicate the St. Louis plant at eight different points scattered throughout the c ~ u m y .A~p~roclamation of the Pres- ident, January 3, 1918, created an Inter-Department Committee 3 to control the manufacture of ammonia, its importation, storage, and dis- tribution, under direction of the Food Admini~trator.~'This control was effective only over the primary producers from coke ovens, gas plants, and even the synthetic-nitrogen operations, so that dealers' prices continued to run riot. During July, these second hands advanced prices 200 to 300 per cent, and fourteen producers of ammonia signed an open appeal to the trade to suppress such unpatriotic profiteers. Among the signers were Barren, General Chemical, Grasselli, Armour, and Morris." After the war the unexpected happened. During 1919 and 1920 +These are 1915 figures compared with 1918. As shown in Appendix XXII, the bulk i ! of the naphthelene produced in the U. S. in 1918 was made by firms not primarily engaged in the operation of coke-oven plants and gas houses. t Frederick W. Frerichs was born in Germany and educated at Godngen where, after receivin his Ph.D., he was asst. t o Wohler, 1874-79. Corning to America in i .i 1880, he was for six years with Mallinckrodt, when he resigned to go into the liquid ammonia business in St. Louis. H e was a charter member of the Am. Inst. Chem. i Engrs., pres., 1911, and treis., 1912-26. t Charles W. Merrill, Food Admin.; L. L. Summers, W a r Ind. Bd.; M. L. Wilkinson Drug Chmz. n/ikts. 12, Jan. '23, 1918.) -,, , THE BY-PRODUCTS FROM COAL I37 strikes in the steel industry, coal mines, and railroads, so curtailed supplies that an actual shortage of both ammonia and sulfate was created. Demand here held up unexpectedly, and similar labor unrest in England so cut its available esportable surplus that an export demand appeared here, which overtaxed our output.'' The cleanup of the war surplus of coal-tar crudes was even more startling. Initially it was assisted by the coal strikes, which took up some slack, but out of these cheap, war-surplus stocks, we created new industries that within a few years were to consume far more basic coaltar materials than the artificial wartime requirements. This transition from war to peace forced many chemical and industrial readjustments. Toluene never reached a fraction of the munitions need. It did, however, find a steady, growing use as a solvent and in coal-tar intermediates synthesis. Accordingly, this ingredient and xylene, too, were commonly left in the benzene fraction. As a solvent for lacquers, rub-. ber, artificial leather, etc., as well as in chemical manufacturing, a market developed for from 10,000,000 to 12,000,000 gallons of this benzol, but ten times that quantity 57 was soon being poured into the gasoline tanks of the motor fuel blenders.* T h e plight of the phenol producers seemed desperate. They had a capacity of more than 100,000,000 pounds a year and the Government held a stock of 35,000,000 poundss6 From $1.00 a pound the price tobogganed to 25& and by 1919 it had slid down to S# a pound. S-pthetic-phenol plants built during the war were being scrapped nght and left. Tar distillers were recovering just as littie as possible. TO help stabilize a critical position, the Government did not advertise its surplus phenol for sale to the highest bidder, but placed it with one of the largest producers, the Monsanto Chemical Works, to be disposed of in an orderly fashion. This surplus was not to be exported, the foreign market being reserved for current output, and the domestic price was fked at 1 2 4 a pound. Phenol seemed to be in a stalemate that promised to last five or six years. Yet within three years several synthetic plants had started up again; a big new plant had been built by the Bakelite Corporation; a new synthetic process had been perfected and put into operation by the Dow Chemical Company. T h e "I think few people realize the amount of work done to pave the way.for this o o t k At times when benzol was in tremendously heavy demand at high prices, and ?hen the petroleum companies were swamped with their own produc4on problems, R was not ")' to arouse too much interest in blending benzol with gasoline a t the unknown future date when the war would be over. I have always considered that one k Y*e m a t effective moves which we made in the Barren Compan durinS the hc of the war production program for motor uewl aosutlheetsawmhnigc-h u-ould Qlx Care ofthe new benzol production after the war was over." (Edward J. h r . author, Jan. 19, 1943.) hPt. .20d .11 -1.50 .1d $$dj 1.45 4.75 .07v .20 75 :30d .12 20.00 .75 .60 .30 .Gdunit -2.50 .om .04 19.00 .la5 .12b 1.50 .M?4 .W%b a. 60 .lo% .a0 .30 30.00 19.00 19 00 i50d -.28 2.60d 3.00 4.50 -2% 3.Bsd 1a2.m00 : so :. a d .04 .07 .06 .08 - .le: 2. Bo 5.50d 13.00 4.50 3.3 :24d DeO. .30 .15 -1.75 .50 .07 .go .61 1.45 4.75 -.13% .75 ..70 12 20.00 .75 .60 .45 .Gunit -2.60 .Ol% .05 19.00 ..1.50 04% 2.65 Nom. .ab .30 .22 0. ..18 04% - 6.00 12.m 1..5m0 .59 .W% .04 .12 .05 .08 .a0 4.00 6. a0 13.25 4..aab 3.1 .30 302 APPENDIXES U. S. IMPORTS OF DRUGS, CHEMICALS, AND THEIR PRODUCTS, 1913-22 (Cont.) Barium sulfate, precipitated (blanc fixe) 1913. . . . . . . . . . 1914. . . . . . . . . . 1915. . . . . . . . . . 1916.. ........ 1917.. . . . . . . . . 1918.. . . . . . . . . 1919.. . . . . . . . . 1920.......... 1921.......... 1922.. ........ 4,808,726 4,752,474 2,233,369 492,723 408,163 179,200 1,285 41,108 1,090,364 3,651,152 $58,499 60,641 25,748 11,523 10,029 2,376 90 1,267 19,291 55,643 Bismuth 1913.. ........ 1914.. . . . . . . . . 1915.. ........ 1916.. ........ 1917.......... 1918.. ........ 1919.. ........ 1920.. . . . . . . . . 1921.. ........ 1922. . . . . . . . . . 151,030 $257,176 131,190 . 241,448 34,237 72,587 64,281 155,925 88,465 196,113 75,611 207,098 76,539 218,376 75,781 97,489 96,692 159,670 97,470 158,760 Bark, scc Cinchona; Mangrove Blanc fixe, see Barium sulfate Bauxite, crude 1913.. ........ 1914.. ........ 1915.......... 1916.. ........ 1917.. ........ 1918.. . . . . . . . . 1919.. ........ 1920.. . . . . . . . . 1921.. . . . . . . . . 1922.. ........ Tons. 30,863 23,576 12,870 3,450 6,403 2,238 2,744 11,748 59,135 11,644 $119,848 86,871 50,557 17,194 22,568 10,045 10,577 77,391 343,909 52,468 Bleaching powder, see Lime, chlorinated Blood, dried 1914.. ........ 1915.. ........ 1916.......... 1917.. ........ 1918.. ........ 1919. . . . . . . . . . 1920.. ........ 1921.......... 1922.. ........ - - -- - 14,281,776 18,457,336 7,412,909 15,085,485 $391,947 227,648 196,600 379,067 479,518 518,630 678,948 290,609 337,349 Bauxite, refined, sce Aluminum hydroxide Beeswax & other animal wax 1913.. ........ 1914.. ........ 1915.. ........ 1916.. 1917.. ........ ........ 1918.. 1919.. ........ ........ 1920.......... 11992221.... ................ 828,287 1,412,695 1,565,338 2,284,283 2,711,514 1,950,513 2,100,458 3,919,810 2,215,332 3,100,971 $ 254,704 477,745 440,047 618,856 904,557 678,148 783,716 1,354,782 693,551 580,723 Benzaldehyde, JCC Naphthol, beta Benzene 1917.......... 1918.. ........ 1919.......... 1920.......... 1921.......... 1922. . . . . . . . . . 3,175,906 3,073,948 1,509,861 170,519 1,717,936 458,949 $273,108 216,640 38,209 2,547 42,537 9,651 Benzine, see Oil, mineral Benzyl chloride 1920.. ........ 1,150 8452 Blues: Berlin, Prussian, Chinese, etc. 1914.. ........ '1915.. ........ 1916.. ........ 1917.. ........ 1918.. ........ 1919.. ........ 1920.......... 275,174 547,299 185,294 373,074 13,867 8,222 297,256 $ 50,149 112,904 110,901 209,524 15,009 5,879 120,726 1921.. ........ 1922. . . . . . . . . . 275,757 20,617 124,204 7,113 Bones, crude, steamed, or ground 1913.. ........ 1914.. ........ 1915.. 1916.. ........ ........ 1917.. 1918.. ................ --- $ 565,566 829,730 756,015 -- 755,700 826,142 - 1,010,871 1919.. . . . . . . . . 26,275,886 369,583 1920.. ........ 94,593,269 1,500,142 1921.. ........ 155,409,170 2,526,323 1922.......... 41,202,190 450,649 Bone black, lampblack, etc. 1913.. 1914.. 1915.. ........ ........ ........ 1916.. ........ ---- $31,056 27,604 24,459 2,396 01. 111, Appendix XX )UCTS, 1913-22 ivailable because ot specially pro- n.e.s. --- - --- --- 3 364,347 357,035 2,611 ,741 22,717,335 54,725,124 5,673 ,707 4,573,969 5,297,987 3,029,332 1,019,671 denatured 232 3 58,346 845 67,728 455 108,985 243 8,784,742 634 16,027,867 142 4,619,878 383 6,145,115 APPENDIXES 327 1920.. ....... 1921.. ....... 1922.. ....... Gallons. 27,376,167 14,635,394 3,180,013 810,455,247 7,569,381 943,774 Alcohol, methyl, see Vol. 111, Appendix XXXIII Ammonium sulfate 1920. . . . . . . . . 1921.. ....... 1922. . . . . . . . . 17,489 65,915 168,077 Tons. 82,264,387 7,620,130 8,720,775 Baking powder, see Vol. 11, Appendix XXXI Bauxite & other aluminum ores & concen- trates 1915.. ....... 1916......... 1917.. ....... 1918.. ....... 1919. . . . . . . . . 1920. . . . . . . . . 1921. ........ 1922. ........ 11,949 19,317 18,495 21,313 18,187 20,890 13,081 19,617 3 531,404 929,309 1,118,777 1,463,842 1,397,200 1,709,390 1,066,732 961,208 Tons. Benzene 1918. . . . . . . . . 1919. . . . . . . . . 1920.. ....... 1921.. 1922.. ....... ....... 25,400,852 24,402,278 17,253,314 66,622,862 55,179,363 $2,152,315 1,236,282 732,836 3,182,721 1,978,776 Bleaching powder, see Lime, chlorinated Borax, refined 1920.. ....... 1921......... 1922.. ....... 10,943,110 4,368,880 10,094,724 3905,617 385,650 545,601 Calaum acetate, see Vol. 111, Appendix XXXIII Calcium carbide 11991134.................. 1915.. ....... 1916.. ....... 1917......... 1918......... 1919.. ....... 11992201.................. 1922.. ....... 33,419,375 32.845.649 35;772',867 37,873,692 31,278,971 28,814,176 21,278,167 21,164,404 20,147.753 12,477;237 3 990,027 962.040 1,097,952 1,211,267 1,001,861 1,327,864 1,537,984 1,040,754 967.024 629,164 Coal tar & pitch 1913.. ....... 1914. ........ 1915.. ....... 1916.. ....... 1917.. ....... 1918.. ....... 1919. . . . . . . . . 1920. . . . . . . . . 1921.. ....... 1922. ........ 121,168 22,150 21,317 74,809 62,674 53,955 60,672 81,640 128,103 76,653 Barrels, 280 Ib. $152,273 43,145 39,647 129,220 145,574 147,765 201,653 192,294 287,300 159,078 Coal-tar distillates, crude, n.e.s. 1918.. ....... - 85,620,851 1919.. ....... - 3,748,370 1920.. . . . . . . . 1921.. ....... 1922.. ....... - 3,618 ,424 - 4,101,129 - 154,983 Cod-tar medicinals 1913.. ....... 1914.. ....... 1915.. ....... 1916.. ....... 1917.. ....... 1918.. ....... 1919.. ....... 1920. ........ 1921.. 1922.. .......:...... ---------- 3 7,110,493 6,721 ,978 7 ,130,379 8,397,971 8,613,202 10,190,188 15,277,037 20,124,561 18,038,328 224,546 Copper sulfate (blue vkriol), see Vol. 111, Appendix XVIII Dye extracts, n.e.s. 1918.. ....... 1919.. 1920.. .............. 1921.. ....... 1922.. ....... ---- 2,614,110 $7,284,110 6,125,394 6,829 ,937 3,571,309 459 ,861 Dyes & dyestuffs 1913.. ....... 1914.. ....... 1915.. ....... 1916., ....... 1917.. ....... - 3 347,656 - 356,919 - 1,775,925 - 5,102,002 - 11,710,887 Stated separately after 1917. Ferroalloys, tungsten, manganese, etc., n.cs. 1917.. ....... 1918.. ....... 1919......... 111999222012........................... 1,784,306 2,184,769 177,123 17,494 1,m 303 33,597,426 4,056,437 408 ,148 57,820 1,625 13,189 In tons after 1921. SALS (Continued) Fordnej-McCumbcr Act, 1916; n.e., not Aspirin. ................. Azides. .................. Barium carbonate, precip.. . chloride. ............... dioxide. ............... hydroxide. ............. nitrate.. ............... sulfate, precip.. Barytes, crude.. ......... ......... ground. ............... Bauxire, crude. ........... ref., ................... Benzalchlonde.. .......... Benzaldehyde, med.. ...... non-mcd.. ............. Benzanthrone ............ Benzene. ................ Benzidine, & sulfate. ...... Benzoquinone. ........... Benzoyl chloride.. ........ Becnhzlyolriadcee.t.a.te.,.&..b..e.n.z.o.a.te... Benzylethylaniline. ....... Bismuth. ................ comp., salts, mixt.. . . . . . Black pigments (carbon, gas, lampblack), n.s.p.f.. ........... Blanc fixe.. .............. Bleaching powder.. ....... Blue pigments, & all with iron fern- or ferrocy- anide. ............. APPENDIXES ........... ........... ........... ................. .............. ........... ............. * Based on Am. selling price of competitive U. S. artide, if none, on U. S. vdue; 7%&! a% after 2 yr., Special Duty Act, 1916; O 7# & 45% after 2 v.,Special Duty Act, 1916; n.e., not enumerated, but rate fixed by d i n g ; na.p.f., not s p e d d y provided for. Ltd. td. [TRATE 20.) M a t e (memc tons) 1912 I 1913 3,000 2,000 70 1,650 3,OOO 5,000 3,000 ?,SO0 7,000 7,000 i,000' .-,300 16,000 45,700 300 2,OOo 97,000 460,000 8,000 33,000 115,000 68,000 75,000. -1,350 ,444 98,557 - -1-,139 26-6,850b ,103 1,286,757 I VOLUME I11 New York D. VAN NOSTRAND COMPANY, INC. 2SO Fourth Avenue 1945 w-e,Jemmm---- COPYRIGHT,1941 BY -D. VAN NOSTRAND COMPANY, INC. All Rights Reserved This boo&, or any parts thereof, may not be reproduced in any form without written permission from the Author and the publishers. PUINTED I N THE UNITED STATES OP A M E R I C A vv an oppormd oranges. Iin 1915 inof which is ric acid was ing the war, cess the em3n the essen- the commersituation and xports estabrestricted to ]-kilo keg of to 700 he.2* certain types, acid."5 Comided on work nent of A@t for Charles f molds built Zharles Thorn wrgillus niger c acid with a 'ocess evolved :ories, the first was no doubt iver the citric IS already rethe Tarifi! of :e list and im- e duty on the evitably, there Iounds in 1913 5.29 With our xing news that vhen hostilities heir future re- rs-WeightmanL situation that :ets throughout SOME OTHERACIDS 53 the war. American manufacturers, much of whose output was sold on yearly contract, endeavored to hold down prices. But the fright- ened overbuying presented a golden opportunity to brokers and secondhand speculators to charge fancy prices for spot material. During August and September 1914, for example, American makers advanced the price of citric acid from 53&to 58l/,4, but the first of the new year they brought it back to 554. Here they held their quotations throughout 1915. Importers' and brokers' prices went to 704 inSeptember 1914 and to 906 in June 1915.' American production grew from 2,729,943 pounds in 1914 to 4,032,897 pounds in 1917,31but it was inadequate to fill expansion requirements-stimulated somewhat by the increased soft-drink business due to Prohibition-so that during the latter part of 1917 the price reached 759, moving quite steadily upwards till the spring of 1919, when a top of $1.25 was touched for a brief period. A year later, the price was down to 404 or actually 104 below the prewar quotation. After the appearance of the fermentation acid the price continued steadily to de'cline, a pretty example a t once of the normal course of price competition between natural and synthetic products,32and the advantage t o the American consumer of a self-contained domestic production of chemicals. Synthetic processes for the production of maleic acid, by the catalytic oxidation of benzene, were patented by John Weks and Charles Raymond Downs, starting in 1919.33 This opened up an entirely new field of chemical synthesis-maleic anhydride; malic, succinic, and fumaric acids-with seemingly bright commercial possibilities. However, the practical application of the entire maleic acid field was not at the time realized. A number of other acids of minor, specialized uses felt the quickening touch of war demand and obstructed supply. Tannic acid34had reacted promptly to a drastic cut in duty from 359 to 5/ in the Tariff of 1913. Impom-aImost entirely from Germany-jumped from 12,892 pounds for the fiscal year of 1914 to 49,493 pounds for the same period in 1915. The price, instead of declining on the lower tariff, advanced from 30-356 in 1912 to 70/ in 1914. During the war years of 1916-18, imports were very light, but in 1919 they amounted to 68,336 pounds. At this time there were four producers in this country: F. Bredt & Company, New York; Mallinckrodt Chemical Works, St. Louis; PowersWeightman-Rosenganen, Philadelphia; and Zinsser & Company, Hasdngs-on-Hudson, New York. Mallinckrodt and Zinsser were also producing pyrogallic acid and were joined during the war by the Eastman Kodak Company. Domestic production which prewar supplied about half of our demands, all See Vol. 11, Appendix 11. 110 INDUSTRIAL CHEMICALS speaking "new" in 1917, yet that year both sprang into national prominence. This destructive pest, which had crossed the Rio Grande from Mexico into the Brownsville area of Texas about 1892,' had spread itself lustily and with little effective check. During 1917, one of its periodically favorable seasons, it flourished exceedingly, devastating plantations as far north as South Carolina at a time when the high price of cotton emphasized the high cost of its damage. That same year the Department of Agriculture spread the welcome news that its laboratory at Tallulah, Louisiana, had found an effective control for the rampant weevil in calcium arsenate.2 As far back as 1907 this chemical had attracted the attention of entomologists who hoped to find it an efficient, economical substitute for the comparatively expensive lead ar~enate.~But the calcium salt burned foliage, especially fruit-tree leaves, and it was discarded till war stringencies spurred in- vestigators at a number of experiment stations again to try it out on cabbage, potatoes, and other vegetables. They found it effective against chewing insects such as the potato and cucumber beetles, the coddling and tussock moths, the webworm, tent caterpillar, and others." Then came the discovery that it was notably efficient against the boll weevil. From almost nothing in 1917, production of calcium arsenate rose to 13,261,233 pounds in 1923, with nine producers reporting to the Census Bureau." This fantastic growth intensified disrupting influences which, as we shall see, always surround the insecticide and fungicide markets. Calcium arsenate was not, however, the only war baby in this chemical group. Indeed it was an orphan left on the industry's doorstep, compared to paradichlorobenzene and chIoropicrin which were both born'in the munitions plants. The chlorination of benzene to produce monochlorobenzene, needed in the manufacture of the explosive, picric acid, accumulated embarrass- ing quantities of p-dichlorobenzene (C,H,CI,) . This by-product was seldom isolated or weighed. In fact, so few manufacturers kept any record of its production that the Tariff Commission Dye Cennrs of 1918 made no attempt to evaluate its output. t In 1919, however, the Tariff Commission reported 130,864 pounds of p-dichlorobenzene valued at 7 # a pound. The following year the D y e Census recorded an output of 465,292 pounds at an average price of 9Qa pound.6 In 1921 the output was 402,289 pounds and the average price was 16#.' Researches of the Department of Agriculture lay behind these figures. In 1915 the Department had approved p-dichlorobenzene as a fumi- Output in 1921 was 2,419,684lb. from 7 producers; in 1919, 1,191,868 lb. from 5. t Producers reporting to the Dye Census that year were: Hooker Electrochemical, Monsanto, Niagara Alkali, Union Dye & Chemical. a inal purposes from verage alcohol from ve placed medicinal iited protests of the for alcohol used in -ease in alcohol taxes :k up before the new campaign was being introduced, the same o avoid higher taxes, reased production of :oh01 market at that ion with consumers I a trainload. lis season to $2.40 a bove any relation to rice and talk in the x-any industrial use, st distilleries the raw .e early frost, which p in the Ohio Valley. ., called a conference hio, which arranged created. In Septemased and in October :t. Alcohol producries met this entirely of U.S.P. ethyl alcoa gallon, dropped to level, thanks to the :slid down to $4.50.39 sed up, however, ennd users of industrial Jolstead Act became ;intent w3s not only sure an ample supply h and in the develop- But its more rabid xcupied with alcohol :mical. They had no usands of things from ALCOHOL: BEVERAGE ~ i i vCHEMICAL 129 TNT and tincture of iodine to transparent soap and artificial flowers. They had, of course, no comprehension that alcohol loaded with such denaturants as benzine, nitrobenzene, and pyridine, was exactly as un- suited for certain chemical applications as it was for beverage purposes. Another group, fearful of violations, did not care what trouble and expense legitimate industry was caused if it could make sure that not a drop of alcohol would be drunk. Consequently the regulations controlling the manufacture, sale, and use of denatured alcohol were extremely onerous. Producers and consumers of denatured alcohol found that under the famous Regulations No. 60 and 61,they were now subject to all re- strictions that had previously hedged in the whisky business, complicated by arbitrary, bureaucratic rulings. T o use any alcohol, three sets of sworn applications had to be executed and a penal bond of not less than $1,000 nor more than $100,000 posted. Makers and distributors were subject to constant supervision and inspection and were required to keep detailed records of every sale. T h e severest hardship was constant uncertainty. The law was administered by regulations, issued and revised at the wiU of the Prohibition Commissioner, interpreted now rigidly, again quite liberally. As the enforcement personnel was constantly shifting, formulas, forms, and records were revised time and again. Unannounced changes, sprung suddenly in a frantic effort to foil bootleggers and "cookers" who were regenerating denatured alco- hol, kept legitimate trade in a turmoil. PT o red ta e were added many ridiculous harassments. Dr. Whitaker, in a talk be ore the New York Section of the American Chemical Society,'O recited some of the difficulties encountered by his own company. The telephone company refused to list "U. S. Industrial Alcohol Co." in its directories unul special permission had been obtained from Washington. T h e Prohibition Commissioner ruled that "Cologne spirits and alcohol, pure and denatured," which had been on their letterheads for fifteen years, was illegal. The Company was forbidden to ship isobutyl alcohol to France till the labels were changed to "Isobutyl Solvent.'' At the end of the war, the familiar fear of overproduction worried alcohol producers. But as in so many other chemical fields, new markets, opened up through technological advances, changed what promised to be painful contraction into still greater expansion. In this respect, Prohibition unwittingly aided the readjustment. It helped persuade many disdlers that the game was not worth the candle. Accordingly, within two years production was cut in half. Curtailed output with Prohibition restrictions and the tax, which amounted to 1,000 per cent of the actual chemical value of the alcohol, created a critical shortage for legitimate consumers. By the middle of `I iI /j I I 111 I I I i 00 gallons a day, for down since the end Bureau of Internal scuss how the acute alleviated." Among os Fries of the ChemD f Columbia Univer;Manufacturers' Asifacturing Perfumers' 2 American Dyes InSociety; and E. C. of Retail Druggists. it, the necessity for a the need of special rovisions of the law; :es to help legitimate I tax on alcohol, now ?ed than similar taxes mical. o r y trade committee D f James M. Doran * 1920. Under his ad.e alcohol trade. H e men and cooperated ies and by the Amer- stark reality between ment of the country, nt was bound to hurt Amendment, alcohoI e, brought to this difficult Jerience with Prohibition ' industry. He performed :nt with legitimate use of Inst. were: H. J. Kaltenbach, Alcohol Co.; G. AI. Mclefferson Distilling & DeAlcohol Co.; Victor M. tucky Distilleries %i WareO.P.D. Reptr. 61, Jan. 24, included Dr. Martin H. 1. Rosengarten, Dr. Frank unison, appointed at the 133 (1922).1 ALCOHOL: BEVERAGE AND CHEMICAL 131 could not be regarded objectively as a chemical. Its natural develop- ment was inevitably warped. Despite these handicaps, the growth of the chemical industry, especially the synthetic organic branch, and the amazing postwar development of the automobile, created new demands for alcohol that were strengthening and stabilizing factors. During the war, Continental countries, cut off from American gasoline, had turned to alcohol as a motor fuel and they continued after the war to supplement imported gasoline with various alcohol and benzine blends. In the United States the threatened overproduction of alcohol suggested this same possibility to alcohol producers. The United States Industrial Alcohol Company, after wrestling with methods of dehydration, offered motorists a 10-90 blend of alcohol and gasoline under the trade name of Alcogas." After two years of disheartening sales effort, the product was withdrawn from the market in 1920. The sound economic reason announced was that anhydrous alcohol cost more than gasoline and the motorist could not be convinced of the advantages of this premium fuel. It was the motorist, however, who raised alcohol to a big-tonnage chemical. The spread of good roads and increasing use of the snowplow made the automobile a year-round means of transportation. Alcohol was the first, and for many years the only, satisfactory anti-freeze. By 1922, motorists were pouring into their radiators more gallons of alcohol than the industry had produced prewar. REFERENCES 1. Lucas, Ancient Egyptian Materials and Industries. 2. Can. Chem Met. I, 79 (1921); P. A. Hill, ibid. 233 ;B. R. Tunison, 1.Frank. Inst. 190, 374 (1920). 3. Hill, op. cit.; Chem. Trade I. 73, 125 (1923). 4. E. Kramers, Dept. Agr., Bull. No. 182 (1915). 5. G. S. Whitby and M. Katz, I d . Eng. Chem 2f, 1209 (1933); L. A. Wood, Bur. Stand. Circ. No. 427, 5 (1940); Haynes and Hauser, Rationed Rubber, 74. 6. grenuss, Chemicals in War, pp. 182, 625, 633. 7. Gilbert's Ann. d. Physik 63, 348 (1819). 8. E. Simonsen, Z . angew. Cbem. 11, 195, 962, 1007 (1898). 9. F. W. Kressmann, Dept. Agr., Bull. No. 983, 11 (1922). 10. Tomlinson, Chem. Met. Eng. 19, 552 (1918); Chem. Trade I. 63, 103 (1918). 11. L. du Pont, to author, Dec. 31, 1943; R. v. Demuth, Z . angew. Chem. 26, 786 (1913); G. Foth, C h m . Ztg. 37, 1221, 1297 (1913). 12. H. K. Benson, Dept. Corn., Nat. Comm. Wood Utilization, Rept. No. 22, 117 (1932). 13. O.P.D.Reptr. 15 (June 25, 1917); Met. Chem. Eng. 17, 101 (1917). 14. I. SOC. Cbem. Ind. 28, 1290 (1909). 15. Kressmann, op. cit. 16. Ibid.; Kressmann, J. Ind. Eng. Chem. 6, 625 (1914), 7, 920 (1915); E. C. Sherrard and G. W. Blanco, ibid. lI, 611 (1923). * Whitaker holds the following U.S. Pats.on alcohol-containing fuel for the internal- combustion engine: 1,405,809, 1,420,006, 1,420,007, 1,423,058 (1922). For account of this research, see A. D. Little, I n d . Eng. Chem. 15, 196 (1923). ! 210 THE COAL-TAR CHEMICALS shipments of coal-tar products were withheld or released.* While it reflected inept Teutonic psychology, Ambassador von Bernstorffs boast that lack of these essential chemicals would bring us to our knees, also revealed their faith in this economic weapon. The Germans overvalued our commercial instincts and underestimated our chemical capabilities. They could not believe that their highly complex, organic syntheses with all their intricate apparatus and all the ingenious know-how which it had taken them half a century to perfect and which they had guarded so jealously, could possibly be duplicated in the United States before the war would be won. No doubt they knew to an ounce our exact output of dyes and medicinals and they appreciated better than we did our chemical dependence, since they sold us practically all our intermediates. They had long since learned that these key materials are the most complicated, expensive products of the entire coal-tar business, representing 85 per cent of the capital investment.2 While they were concerned over our rapidly expanding production of high-power explosives, TNT and pic- ric acid, they found comfort in this military use of benzene, toluene, and phenol. This lucrative munitions business, they reasoned, would shoulder aside attempts to manufacture other, more difficult intermediates. With no intermediates, no coal-tar industry could be built up. Only a few American chemical men foresaw the obstacles ahead, but many people far outside chemical circles promptly recognized the menace of a coal-tar chemical famine and realized that something must be done about it. The swift rush of German armies toward Paris had not been stopped at the Marne before the Secretary of the Interior summoned a score of chemical manufacturers to the first coal-tar conference, September 3, 1914.t Secretary Lane propounded the question of what the Government could and should do to promote a domestic coaltar chemical industry. This then-novel proposal called forth a different response from almost every man in the room. Among the hodge-podge of opinions there was agreement on only one point. The "wasteful beehive ovens" were properly ~astigated.~Nothing definite was accomplished, but the problem was posed and the intimate relationship of For details, see Vol. 11, Chap. 3. tif.t Present were Henry Wig lesworth, General Chemical; Thomas S. Grasselli and G. E. Fisher, Grasselli; John Schoellkopf, Schoellkopf-Hartford-Hanna Co.;Alfred L. Lustig and John Bancroft, Nac. Assoc. Finishers Cotton Fabrics; Donald McKesson, McKesson & Robbins; T. M. Rianhard, American Coal Products; David W. J a p e and Robert P. Perry, Barren;August M e n , Heller & M e n ; I. F. Stone and Jesse W. Starr, Naaonal Aniline; G. N. Cherrington, Charles H. Goddard, American Druggists' Syndicate; H. W. Jordan, Semet-Solvay; Frederick and George D. Rosenganen, Powers- Wei htman-Rosenganen; and Clarence I. Robinson, Standard Oil. (See O.P.D.Reprr. 33, g p t . 7, 1914.) d.# While it nstorffs boast bur knees, also md underestitve that their apparatus and f a century to d possibly be won. : of dyes and chemical detdiates. They x complicated, jenting 85 per :med over our TNT and pic- izene, toluene, asoned, would x l t intermedid be built up. bstacles ahead, recognized the omething must ward Paris had e Interior sumoal-tar conferthe question of domestic coalx t h a different Le hodge-podge T h e "wasteful efinite was acrelationship of s S. Grasselli and Xanna Co.; Alfred Donald McKesson, wid W. J a p e and .nd Jesse W. Srarr, 1 Druggists' Syndisenganen, Powers(See O.P.D. R e p . FOUNDATIONS OF A NEW INDUSTRY 211 coal-tar crudes and intermediates to explosives, dyes, and medicines was made clear. These fundamentals were expounded shortly afterwards by a special committee: Bernhard C. Hesse, chairman, John B. F. Herreshoff, I. F. Stone, J. Merritt iMatthews, Herman A. Men, David W. Jayne, and Allen Rogers. Appointed by the New York Section of the American Chemical Society, November 6, 1914, to investigate the coal-tar chemical situation, this representative group summarized its findings: There is no inherent defect in our coke industry with regard to the actual making of these things; the only question involved is whether it be more profitable to burn the benzol, toluol and the like contained in the gas as fuel than to separate them from each other for purposes of sale. The materials of the preceding paragraph are the ones used in the coal-tar explosives industry as well as in the coal-tar medicinals and dyestuffs industries. Each of these three industries cooperated with the other to make full use of those materials; alone none can fully make use thereof nor succeed; . .the correct and proper utilization of these materials requires successful co- existence of all three industries in one and the same country. .* This excellent report was widely publicized in the technical press and newspapers and it was read in full to the House of representative^.^ Thus at the outset the coal-tar case was well defined. News from the front of critical ammunition shortages and firsthand experience with the lack of dyes and medicines were needed to rouse the interest of the general public. But the facts were faced squarely in Washington and by the chemical industry. Furthermore, it was tacitly agreed that while as a strictly defense measure the Government might legitimately encourage the installation of additional recovery ovens by contracting to purchase their byproducts, it could not directly or indirectly subsidize any production of other coal-tar chemicals. The Army and Navy ignored these plain warnings and improvidently failed to anticipate munitions requirements for toluene and phenol. Not until we were actually at war, three years later, did they encourage the coal-tar expansion by means of such pur- chase contracts. As for the other branches of the synthetic organic industry, these stood from the first on their own feet. Coal-tar chemical manufactbe in this country, therefore, provides an example of free enterprise establishing an ultramodern, technical type of enterprise." By loosening the stranglehold of the German Dye Car- tel, the-war created the opportunity and furnished the incentive. Because of the highly technical character of the industry, initial costs and wstes were enormous. The risks, too, were exorbitant. Along with For U. S. producers of coal-tar finished products, 1917-22, see Appendix XLVIII. ,- el and adequate iere always re;back an expeof the past on Administration, into production trge investment; dardized, yields arket and estabset to meet the vould wipe out s moreover the back and drove Jelled lavish exof our synthetic if we see it as a rs for explosives in the hands of t German dyes The same hurpleted the stores these, since Ger,ts soon stopped. :rmediates. T h e x s packed every riced colors and :diates, Germany e from any con, cut off from its in, had good use -the last regular larch 19, 1915me 300 different coal-tar products mly about threexes used for the harmaceuticals, as i cotton printing. November 1916, did FOUNDATIONS OF A NEW INDUSTRY 213 These sixty-odd intermediates had sufficed for the preparation of the limited line of dyes and medicinals then made here. Among the seven American makers of dyes only one, Schoellkopf, was producing any intermediates: T w o fine chemical manufacturers with close German connections, Heyden and Fries Brothers, were producing salicylic and benzoic acids. Monsanto was making chlorosulfonic acid from which to prepare saccharin.' Only one American chemical company, Benzol Products, made any pretense of being a real producer of coal-tar intermediates and its claims were not very impressive. Aniline and nitrobenzene of good quality were being produced,* but though strongly backed, the Company could not meet foreign competition. The three cooperating companies behind this venture did their best to make it a commercial success. SemetSolvay furnished crude benzene at cost; Barrett refined this for operating costs only; General Chemical supplied sulfuric and nitric acids at a price that just covered manufacturing plus overhead charges. Nevertheless, the low- est price Benzol Products quoted was always ~ n d e r c u t . ~ T o the Germans such underselling was good business if it prevented the setting of the intermediate keystone in the coal-tar chemical arch. It might cost them something to absorb the tariff, but it would be a temporary loss onlyand they might always raise their prices in India or China to compensate for reduced profits in the United States. Even if heavy losses had to be taken in enforcing this plan of strangling Amer- ican intermediates makers, the Germans would have not hesitated, for they knew very well that if one competitor survived, the variety of intermediates made here would surely increase and the production of dyes and medicines would inevitably follow. Our dependence upon German intermediates dated back to 1883, when Congress, following blindly the policy of admitting raw materials free to encourage domestic manufacturers, placed this group of chemicals on the free list. T o make matters worse, the basis of duties on finished dyes was changed from specific to ad valorem. T h e tariff margin thus created was sufficiently large, in a number of instances, so that to import the intermediates and complete the manufacture of the dyes in this country became profitable.'O T h e tariff revisions of 1897 and of 1909 continued this policy which played right into the hands of the German dye interests and which they adroitly fostered." (6German manufacturers did not want to supply intermediates to the U. S., yet they were cognizant of the fact that there were other uses for intermediates than in dyemaking, as, for instance, beta-naphthol, which you mention in the case of the Con-a-lap Company. They knew that these other uses would have to be supplied, otherwise h e n c a n s would seek ways of manufacturing, just as Calco did later on, but the v m e v and the quantities shipped to the U. S. were closely watched and carefully conmlled. This is not a matter of hearsay because, as you probably recall, I was FOUNDATIONS OF A NEW INDUSTRY 215 and some of the simpler nitro and amino compounds of benzene and toluene." A throng of rivals began hustling into the coal-tar chemical business. In makeshift plants, equipped with odds and ends of secondhand apparatus, all sorts of people launched forth as makers of intermediates. By cut-and-try methods, complicated, often dangerous reactions were being attempted. Buildings and equipment had to be con- tinually revamped and rebuilt. Fires and explosions were commonplace occurrences. Many lives were lost; much property was destroyed. The yields obtained were often pitifully small and the quality so poor that the early products were virtually unusable. In this mad scramble many fell by the wayside and their losses were liquidated, but the capable, backed by adequate financial resources, gradually came to the front. Among these were naturally the established companies with expeience. T h e Barrett Company-A. G. Peterkin, Jr., John M. Weiss and C. R. Downs shared in this development-added nitronaphthalene and alpha-naphthylamine. Niagara Alkali and Hooker Electrochemical produced the useful chlorobenzene, and in neighboring Buffalo the Schoellkopf staff, D. W. Bissell, C. G. Denck, and R. A, Nelson, and others developed processes from this chlorobenzene to o-nitroanisole, a-anisidine, and dianisidine. Monsanto research under Louis Veillon, Gaston DuBois, and Jules Bebie, prepared a-toluenesulfamide, p phenetidine, and other intermediates, for John F. Queeny had learned the bitter lesson of dependence on foreign sources of these key materials. He was one of the first American manufacturers to insist that his company build its operations upon the solid foundation of intermediates which it produced and whose quality, cost, and supply it controlled. Among those entering the chemical field after 1914, who rated the intermediates rightly and based his chemical operations on them, was Robert C. Jeff cott," a manufacturer of high-grade wall-covering fabrics. He was shoved into chemical manufacturing by the color famine. Like thousands of other American manufacturing firms struggling to keep plants running with vanishing raw materials, his Cott-a-lap Company was hard pressed. Due to the British Government commandeering of jute cloth for use as sand bags, the Company's basic material was only obtainable from Scotland and that with increased difficulty; its supply of German dyes Was being cut off; beta-naphthol, which was used as a mold preventive, *After graduation from Yale in 1897, Jeffcott was for 10 years with General Electric, founded Con-a-lap in 1906, and Calco in 1915. He was strong protagonist of adequate protection for coal-tar chemicals and among many services to the industry Was pres. of Am. Dyes Inst. during the critical years, 1920-22. He continued as active head Of ~ C tilOl 1939, when, upon his retirement, it became the Calco Div. of American Cyanamid, with which it had long been affiliated. 218 THE COAL-TAR CHEMICALS . States Coal-Tar Products Company, New York City; Seydel Manufac- turing Company, Jersey City; the Chemical Company of America, Springfield, New Jersey; Butterworth-Judson Company, Newark, New Jersey; American Synthetic Dyes, Inc., Newark; Middlesex Chemical Company, Chester, Connecticut. In 1915 an important factor in the American coal-tar chemical industry entered the field modestly with a production of phenol for the French Government. The Newport Mining Company, affiliated through common ownership by the Schlesinger family with the Milwaukee Coke & Gas Company, built at Carrollville, Wisconsin, on Lake Michigan, a phenol plant that was soon expanded to produce other intermediates. The idea of working up the benzene and toluene byproducts was first proposed by John Wallace Schaeffer, who was super- intendent and later manager of the Milwaukee Coke & Gas Company, and he engaged John R. M. Klotz from Barren's Frankford plant as manager of the new operation. T o phenol was added alpha-naphthyl- amine, toluidine, and benzidine. In 1915 the Newport Hydro Carbon Company was incorporated in Maine with a capital of $500,000 by Ferdinand and H. J. Schlesinger, Edward G. Wilmer, Roger V. Snow, and Ernest M. White to take over this operation.24 The Company's name was soon changed to the Newport Chemical Works, and in 1917, when the plant was greatly enlarged, such important intermediates as p-nitrotoluene, 0-, and ptoluidine, nitronaphthalene, H acid, and 1:3 :6 acid were added." Under the chemical direction of Dr. Ivan Gubelmann," a Swiss who had come to this country to join several of his fellow-countrymen at Monsanto, a line of dyes was developed. By the close of the war Newport was fairly launched and adopted the slogan "Coal to Dyest&" to emphasize that it was the only manufacturer controlling every step in its operations, from the mining of coal to the shipment of finished colors.2e After the war, when Newport bought out the American Color Manufacturing Company with a small plant in Passaic, its presi- dent, Elvin H. Killheffer,t took over the business admini~tration.~~ 'Educated at the Federal Technical U., Switzerland, Gubelmann was res. chem. with Monsanto, 1912-16, when he became chief chem. of Newporc. After du Pont took over Newporc in 1931, he was left in charge of the Canollville plant for a year, when he moved to Wilmington as chem. dir. of the Organic Chemicals Div. Besides his outstanding work in developing the Newport dyes, he has made conspicuous contributions to perfume bases, photographic chemicals, and synthetic camphor. t Killheffer played a prominent part in the establishment of the dye mdustry. H e was trained at the Phila. Textile Inst. and U. Penn. H e was then chem. for Southwark Mills and later chief chem. in N. Y. for Kalle & Co., which provided another year's training in Germany. In 1915 Killheffer organized the Orient Trading Co. and went to China, procuring large quantities of dyes then much needed in the U. S. On his return he founded the American Color Mfg. Co. H e was pres. of both New- 220 THE COAL-TAR CHEMICALS the new product must be a consumer of iVerrimac's acids; it must be fairly complicated and difficultto produce in first-class quality, so as to discourage competition; it must be a product used in fairly large quantities and in steady demand. The product that seemed to best fulfill these specifications was H acid. We decided to undertake its manufacture, first, of course, in our research laboratory; second, in a small-scale plant in our technical laboratory; third, in a full-sized commercial plant. This program took the better part of a year, so we decided to offer nothing on the market until our product was fully equal to the best imported before the war. When we were finally ready, the price had advanced to about $1.50 a pound and we were able to make money from the start. At the same time a program of research was started covering each step in the process, so that as prices fell, we were able to continue the manufacture as a reasonably profitable business. Later the plant was moved from Woburn to Everett, Massachusetts, and with the acquisition of Merrimac by Monsanto, an enlarged and improved plant was constructed at Everett in the old Merrimac Works, where it is undoubtedly running full capacity today (1942).' This country's direct participation in hostilities had less effect upon intermediates than on crudes. Benzyl chloride, produced only by the Chemical Company of America, and in very small quantities,28 was needed for the manufacture of the tear gas, bromobenzyl cyanide;29 benzyl benzoate and benzyl acetate were in demand for airplane dope."O But there was no dominating demand for intermediates comparable t o the need for toluene and picric acid for explosives. Nevertheless, military requirements created serious shortages, not only of the crudes, benzene and toluene, but also of other chemicals essential in the manu- facture of intermediates. Sulfuric, nitric, and acetic acids, ammonia, methyl alcohol, chlorine, and caustic soda were all commandeered. On the other hand, our entrance into the war made it possible for American chemical manufacturers to make use of German-owned United States patents. The Trading-with-the-Enemy Act, passed OC- tober 6, 1917, authorized the Federal Trade Commission to license patents owned by enemy aliens. While the incomplete or deceptive specifications of these patents made them of limited value, American companies might now research both products and processes with reasonable security against German patent suits after the war. It was a new, simpler process for the manufacture of phthalic anhydride that was to be the most important coal-tar development of the war period.^ Cheap phthalic anhydride was to prove a most fruitful intermediate, for phthalate plasticizers made a great contribution to FOUNDATIONS OF A NEW INDUSTRY 221 of other notable chemical triumphs: new processes for anthraquinone and benzoic acid, and commercial development of the glyptal and rezyl synthetic resins. At the time of the war, phthalic anhydride was important in the preparation of the pharmaceuticals phenolphthalein and benzoic acid, of indigo, of eosin and rhodamine dyes. Our needs for this intermediate were filled by imports of some 50,000 pounds, but its real chemical importance was attested by a German ourput, chiefly by Badische for the preparation of indigo, estimated by Gaston DuBois of Monsanto, at "possibly I 0,000,000 pounds." s2 The Monsanto Chemical Company, which had been making phenolphthalein and benzoates, undertook the difficult task of producing phthalic anhydride by the German method.' This consisted of treating naphthalene with concentrated sulfuric acid in the presence of mercuric sulfate, a delicate operation. To be economically feasible, it required reconversion of the escaping sulfur dioxide gas into sulfuric acid for re-use. Monsanto worked out this ' process, but the price was high, $4.00 a pound. During 1917-18, a process discovered by Dr. F. Frank, a Heidelberg graduate, was in production at the Catalytic Chemical Company,""West Berkley, California. Exaggerated claims were made. "We are shipping large quantities of phthalic anhydride to England, France, Italy, and Switzerland," Dr. Frank declared in a statement to Drzlg 6 C6m'cul Markets, April 10, 1918. "We are manufacturing phthalic anhydride . .here under my own process since about two years, and have operated a large plant day and night . and our output today is more than six times greater than when we began operations. While phthalic an- hydride before the war and until recently has been used chiefly in the manufacture of dyestuffs and medicinal preparations, it now goes into the manufacture of condensites and artificial resins in overwhelming quantities, so that its use for ante-war purposes has become of secondary importance." Whatever might be said about the practicality of his process, one can cordially admire the vision of Dr. Frank's prophecy. In the Color Laboratory, set up by the Bureau of Chemistry to assist in the development of American-made dyes, Dr. Harry D. Gibbs and Courtney Conover had been working on the same problem since the "Before the war Heller ti Men. and Monsanto were about the o d y regular users of phthalic. T h e price was close to 30$ per lb. in 1913-14, and we sold a cask to the Condensite Co. ac about that figure. They never used it and we bought it back at $6. A Newark maker of phenolphthalein is said to have later paid $14 a lb. for that same cask. Besides Condensite, General Electric was interested in phthalic anhydride before 1914, and if my memory is good, we sent them a sam le. A Dr. L. H. Friedburg, h"ucror in chemistry at C.C.N.Y., had observed the formation of a resin, or what have YOU, by condensing glycerin and phthalic. This was probably the start of the glYPm1 resins. but you are right that this development had to await cheap phthalic." (August M e n , to author, Dec. 28, 1942.) c \ Chapter 17 THE FIGHT FOR SURVIVAL CHEMICAL ALLIANCE AND WAR INDUSTRIES BOARD MOVE TO ASSIST DYEiMAKERS-THE NATIONAL ANILINE CONSOLIDATION-DU W N T ENTERS THE DYE FIELD-DOW PRODUCES INDIGO AND NATIONAL AMLINE, ALIZARIN-EMERGENCY TARIFF PASSED AND TARIFF COIMMISSION CRWTED-THE FIRST DYE CENSUS, 1917-DYE NIANLIFAC'TURERS A T DEALER3 FOaM SEPARATE TRADE ASSOCLATIONS. AFTER APRIL 6, 1917, when the United States declared war on Germany, military necessity was injected into the dye crisis. It reshaped the situation and presented the dyemakers with new problems. The desperate need for colors was shouldered aside by an imperious call for explosives. Scarce supplies of essential raw materials suddenly became niggardly quantities, commandeered for the armed forces, controlled by the War Industries Board. Within a few weeks the demand for dyes concentrated acutely upon Navy blue and shades for khaki and olive drab. O n the broader chemical stage, nitrogen stole the limelight of public attention, and in Congress the earlier patriotic enthusiasm for a self-contained American coal-tar industry evaporated and was replaced by partisan politics. In one way only were the dyestuff manufacturers heIped by our belligerency. The Trading-with-the-Enemy Act, October 6, 1917, empowered the Federal Trade Commission to issue non-exclusive licenses to use patents owned by enemy aliens, a useful lever to loosen the German stranglehold. In the war effort the output of toluene, benzene, and phenol increased greatly. But it was possible to divert only a trickle of these essentials to the dye plants. Both the War Industries Board and the Chemical Alliance recognized the gravity of this impasse and each acted to alleviate the bad effects. T h e problem was to supply dye manufacturers with enough raw materials to encourage their splendid progress so as to get the necessary dyes for the textile mills without subtracting more of these critical raw materials from the manufacturers of explosives than was absolutely necessary.' The Chemical Alliance formed a Dyestuffs & Intermediates Section, -assessing members $100 each towards expenses, and electing the follow- ing committee: Dr. Charles L. Reese, du Pont, chairman; Dr. J. Merritt Matthews, Grasselli, secretary; William T. Miller, National Aniline; J 7An ident, C. Fahl79,* and phenj and German aced the couns had expired: )form (methyl tdimethylmeth- Others, howwere still probarbital), Ato11 (phenobarbis; became pro- th H. A. Metz aimed that the intipyrine, Pyrd medicinals t o tant. T h e sole 3untry." iecessity. T h e zyl chloride, all By 1917, when all of these im,es. any firms, some nt of medicinal rican Chemical but erratic lead)ed out by fire; in the adjoining I t College Point, , where the re- :rs Association.2' merican Chemi- berg discovered the I the laboratory and Omdo&, my old : unwashed hands." his "story" are told la1 compounds were Iuncil, of which Dr. rsicians and licensed 1, 1969 (1918).1 COAL-TAR MEDICINALS 317 cal Corporation of New Jersey, with a capitalization of $2,000,000, and B. J. Greenhut, E. R. Wollner, and Herman Erb as d i r e ~ t o r s . ~W~hile principally manufacturers of aromatic chemicals for the soap and per- fume trades, the Commonwealth Chemical Corporation, after it ac- quired its plant at Newark, New Jersey, in the fall of 1916, went rather extensively into the chlorination of toluene for conversion into benzyl alcohol, benzaldehyde, and benzoic acid.'* During the postwar depres- sion Commonwealth was taken over by the Mathieson Alkali Works, which had supplied it with chlorine, and later transferred it to Mon- santo.2s Less pretentious, but persisting to this day, Herman Seydel * entered the benzoate field during the war period. In 1904 he had started the Seydel Manufacturing Company to make textile chemical specialties. During the war, starting with benzoic acid and benzalde- hyde, he began the manufacture of benzoates. On reorganization of the company and change of name to the Seydel Chemical Company, in 1922, the enterprise concentrated on a line of benzoates and other pharmaceutical specialties. One of the most important medicinal intermediates, salicylic acid, starting point for acetylsalicylic acid, was further enhanced by the ex- tensive use of sodium salicylate in medicine and of methyl salicylate as a substitute for natural oil of wintergreen.26 Its preparation from phenol was undertaken by a number of important companies almost immediately after the start of the war: Merck, Semet-Solvay, and Hey- den. During 1916 the Aema Explosives Company began manufactur- ing this acid, but promptly discontinued.zT The Synthetic Products Company of North Tonawanda, New York, was another short-lived producer, but by 1917 du Pont-its salicylic acid plant was destroyed by fire in December of that year 28-Calco, Monsanto, and Dow were also in production and several were making acetylsalicylic acid and methyl salicylate. Merck & Company was very active in this field. Almost immediately after the outbreak of the war, a new plant was built a t Rahway, New Jersey, for the manufacture of coal-tar medic- inals, with T. H. Davis, formerly with the Bayway Chemical Com- pany, in charge of The Middlesex Chemical Company, t which had revamped an old essential oil factory in Chester, Connecti- cut, formerly owned by Percy C. Magnus of Magnus, Mabee & Rey- ' A delightful Belgian, always more the organic chemist than the manufacturer, Seydel came to the U. S. for Kalle in 18%; 1899, Southern sales representative of the Berlin Aniline Works. In 1904 he branched out for himself, with his brother Paul. a recent graduate (D.Sc.) of U. Brussels. When the Seydel Chemical Co. was formed, Herman Seydel began s ecializing in medicinals. In 1914 his brother took over the textile chemicals in the Lydel-Woolley Co. at Atlanta. t Capitalized for $1,OOO,oOO, of which $ZSO,OOO was preferred and the balance common stock. COAL-TAMR EDICINALS 321 familiar phenomenon appeared that when American makers got into production the price was lower'than the Gernians had previously secured. Luminal (phenobarbital) was another sedative manufactured by several firms, which returned afterwards to one company, the Winthrop Chemical Company, operating under the Bayer patents." Novocaine, known as procaine since the war, became almost unobtainable during 1915.'* This Hoechst product was another of those which the Mea: Laboratories undertook to produce and which at the same time the Federal Trade Commission licensed to Rector and later to A b b ~ t t . N~o~vocaine had always been popular in dental practice and 75 per cent of the supply at that time went into this field. A difficult and expensive chemical to prepare, Abbott and Metz alone persevered after the war and most of the output came from mer^.^^ T w o new groups of chemicals in this field attracted attention during the war period. At Johns Hopkins, Dr. David I. Macht* confirmed the fact that the benzoyl group (C,H,CO) in cocaine was necessary for its anesthetic properties. As a consequence, benzyl alcohol and its esters, notably benzyl benzoate, were exploited as substitutes for this narcotic.s6 These products, which were exhibited at the Chemical Exposition of 1918 by the Seydel Manufacturing Company, had previ- ously been used only as perfume materials. During the war a consider- able quantity of both went into the manufacture of airplane Ammonium and zinc valerates had quite a vogue in the treatment of shell shock and the Hanover Chemical Company undertook their pro- d~ction.~' No other commodity whose price was studied by the War Industries Board scored so sensational an advance-SO times the prewar quotationas did a~etphenetidine.'~In the catalog of the Bayer Company for 1915, a U.S.P. grade of this material was listed at $1.50 a pound, but under its trade-mark name, Phenacetin, a t $4.00.'' The basic German patents had expired in 1906, and shortly afterwards, Monsanto began to manufacture acetphenetidine from imported p-phenetidine. But the war shut off the imports and it was some time before Monsanto could undertake the manufacture of all the intermediates leading up to p- phenetidine, including benzene, nitrochlorobenzene, and p-nitrophenetole, so that when we entered the war we were dependent upon imported supplies.Bo There were considerable stocks of acetphenetidine in this country. "Dr. Macht, who was born in MOSCOW, Feb. 14, 1882, returned to Johns Hopkins 1902; M.D., 1906) in 1908 to teach pharm. for 10 years and later to lecture on clin. pharm. (1925-32). He has been dir. of the pharm. res. lab. of Hynson, Westcott & Dunning since 1925, where he has carried on his extensive, original studies in the field of toxicology. ,I but once started, 'on the appearance $20.00.61 Various Pont, Merck, and :fact that during lent bought 7,125 .ecline. After the is, used to reduce so acetanilide, reoal-tar medicinals. etanilide had long 1 per cent of our : due partly to an )m there, and the ' acid.e4 Between :nment purchased it for 1917, 1918, .cached 1,255,140 moduced by Mon4cKesson & Rob- :rade-named Atoose use increase$ nufacture in t h s ictually produced mthesis, and later American rights iophen, the ethyl d, was also synT01ysin.~~ I, cascara sagrada, . phenolphthalein. :rally to increase :a1 drugs, despite ierties of phenolan indicator and tde from pomace, : which were by . Peasants living :d and consumed lisease. Medical ited clinical tests COAL-TAR MEDICINA~S 323 that established its cathartic properties." Again, Monsanto was a pioneer, but by 1917 there were three other producers-the Catalytic Chemical Company of San Francisco, McKesson & Robbins, and the Youngstown Chemical Company. Barrett also produced some phenol- phthalein in 1917,'' and later Charles Pfizer & Company. The Newport Chemical Works made good the deficiency of guaiacol, in the liquid form, from which the official preparation, guaiacol car- bonate, trade-named by Bayer, Duotal, was prepared. This company underwrote a special pharmaceutical research by Linda Winkelblech and R. E. Kremers, who prepared guaiacol phenyl urethane, and other guaiacol derivatives.88 Guaiacol crystals were also prepared by du Pont and Newport, and the Seydel Manufacturing Company produced guaiacol benzoate, a new product." Amid the high-pressure war work, surprising progress was made in this country in coal-tar medicinals. Following up the research work of Dr. Macht on benzoates, A. D. Hirschfelder and coworkers at-the University of Minnesota found salicyl alcohol (saligenin) a useful local anesthetic,Be and Roger Adams and Oliver Kamm at the University of Illinois, with E. H. Volwiler of Abbott Laboratories, discovered B u t p (p-aminobenzoyl-N-dibutylaminopropyl sulfate) to be in the same class.70 In 1922, through the work of Raiziss, Abbott introduced Meta- phen, a mercuric germicide.?' A preparation of this type, Mercuro- chrome, which was widely sold, first came on the market in 1919 from Hynson, Westcott & Dunning. t This discovery rose from the suggestion of J. T. Geraghty and Dunning in 1912 that the dye phenolsul- fonphthalein, first synthesized by Remsen and used as a diagnostic in kidney disease, might have useful properties if combined with an anti- septic H. H. Young of Baltimore made this combination and got Mer~urochrome.~T~he World War I antiseptics, dichloramine-T (p-toluenesulfondichloramide) , chloramine-T (sodium p-toluenesulfonchloramide), and halazone (p-dichlorosulfamylbenzoic acid), were prepared in this country by Abbott, Monsanto, Calco, and after the war E. R. Squibb & Sons made the first two compounds.$ Even in the hurly-burly of the war effort, the distinction of coal-tar dyes and medicinals was remarkably maintained among the manufac- turers. The interlocking of crudes and intermediates always prevents complete separation, and du Pont, National Aniline, Calco, Newport, even Sherwin-Williams and Grasselli, appeared among the makers of synthetic drugs or their intermediates. In the main, however, a distinct See Appendix LX. + Be!$nning with 1926, this company manufactured Mercurochrome under license of (2. White's U.S. Pat. 1,535,003 (1925), which had been fled July 26, 1921. See Appendix LX and Chap. 19. istry at Johns Hopkins, and Martin H. Itmer found the missing link to be hydroxyciuonellal; successfully prepared it; passed on the in- formation to an American chemical manufacturer for commercial pro- duction. Ittner * also worked out a practical synthesis for phenylethyl alcohol and George Peirce, his assistant, by adopang the Grignard reac- tion to a large-scale reaction, produced ethyl citronellol t commercially. For a time, this product was manufactured, but later it also was turned over to another manufacturer. The month before the war, July 1914, F. E. Stockelbach, Willard A. Walsh, Carl Schaetzer, and Warren E. Burns bought up the almost defunct business of T. 3.Grossmith and organized the Commonwealth Fruit Products Corporation to manufacture fruit juice concentrates for the soft-drink trade. The war switched this enterprise into the manufacture of organic synthetics, the first products being methyl ionones, rhodinol, and geraniol. By 1916 the toluene products, benzyl I acetate, benzaldehyde, and benzoic acid were added, and the company's name was changed to the Commonwealth Chemical Corporation. Dr. Eric Clemmensen, many years in the research department of Parke, Davis & Company, came as the head of the laboratory established in the new small plant acquired at Newark, New Jersey. The interests of Burns, Schaetzer and Walsh$ were bought out by Stockelbach and 4 Clemmensen in 1918, when the manufacture of malachite green was undertaken. After the war, production centered more and more upon benzoates and coumarin. In 1922 Commonwealth was taken over as a division of the Mathieson Alkali Works and later sold to Monsant0.2~ Another early newcomer was the Florasynth Laboratories, organized in 1916 by Louis A. Rosett and Charles L. Senior, who had been a salesman with Van Dyk & Company.2s At the Chemical Exposition in 1920, Florasynth exhibited benzyl benzoate, phenylacetaldehyde, anisaldehyde, isoeugenol, linalyl acetate, and methyl anthraniIate.26 In 1918 this company became the American sales agents for Schmoller & Bompard of Grasse and functioned more as a specialty than a chemical he held until his death, Apr. 22, 194s: H e had: tremendously constructive gfluence, not only on his own company, but on the whole cosmetic industry. H e was pres. of the Am. Inst. Chem. Engrs. and the Chemists' Club (N. Y.), and held an hon. D.%. from Colgate U.,1930, the Modem Pioneer award of the Nat. Assoc. Mfrs., 1940, and the Perkm medal, 1942. t ``AS far as Dr. Reid making ethyl citronellol, there is no doubt about it that he made it. But Van Dyk & Co. sold ethyl citronellol long before the war. As a matter of fact, we had one customer that took all our production. Ethyl citronellol is made by the Grignard reaction but we never produced it on a large scale. T h e most we made was 100 pounds a month." (S. Isermann, to author, Feb. 20, 1945.) X These men subsequently organized Morana, Inc. Chapter 24 CHEMICALIZATION OF INDUSTRY WAR STIMULATES CHEMICAL PROCESSING I N MANY INDUSTRIES-PAPER MILLS MAKE O W N BLEACH AND DEVELOP THEIR CHEMICAL. WASTES-ACCELERATORS AND ANTIOXIDANTS IN RUBBER COMPOUNDING; AMERICAN EFlWRTS TU SYNTHESIZE RUBBERU. S. WINS OPTICAL GLASS INDEPENDENCE; PYREX 1NTRODUCED-SY"METIC TANSTUFFS COMPETE WITH NATURAL-CHEMICAL. RESEARCH I N FOODS-PIONEER REFRIGERANTS. IN THE AUTUMN OF 1918, when the vaunted German war machine collapsed unexpectedly, completely like the one-horse shay, the American chemical industry was caught overextended Band without lans for reconversion. Large stocks of all the basic chemicals-so a ash and caustic soda; sulfuric, muriatic, and nitric acids; alcohol and methanol, acetone and acetic acid; chlorine; acetylene; the recent coal-tar additions, benzene and naphthalene; aniline and phenolhad accumulated. Installed capacity for production of dl these breadand-butter chemicals far exceeded the high mark of any prewar sales. Hundreds of new products were being made by every branch of the industry. The only exceptions to a stunning chemical overproduction were a few items we had always imported, notably potash salts and the coal-tar crude, anthracene. Every chemical company had expanded its capacity and added new products. A whole herd of new producers had rushed into the field. According to the compilations of a financial newspaper, new chemical companies with an authorized capital of $400,210,000 had been incorporated during the period of actual hostilities.' Many of these were war-born opportunists certain to scrap their operations promptly. Others, financially weak or technically incompetent, plainly were destined to be forced out of the business. But in every field there were =vera1 strong newcomers obviously able and determined to hold fast to their war-won positions. Whether one calculated plant capacity or counted the number of producers, the answer always added up to an CXCess Over any anticipated peacetime demand. h h o s t unanimously the leaders of the industry were apprehensive. A rough period of reconstruction seemed the unavoidable prospect. Ivar contracts canceled arbitrarily by the Government meant more than an abrupt loss of direct orders. Following this example, textile, PPery leather, steel, glass, paint, in fact all manufacturers, repudiated 353