THE CHEMICAL A N D CHEMICAL PROCESS INDUSTRIES Compound S for the preparation of corti sone. The search for other new approaches to the synthesis of cortisone and Cornpound F continued to occupy the atten tion of a number of chemists, and several new methods were described during t h e past year. Two synthetic estrogens, with fewer side effects than the natural prod ucts, wer : introduced. The compounds are tri-p-anisylchloroethylene and 2,2dimethyl - 3 - ( 6 - methoxy - 2 - naphthyl ) pentanoic acid. Several groups reported obtaining ho mogeneous preparations of corticotropin ( ACTH ). Vasopressin, prepared from the posterior pituitary glands of hogs, was round to contain L-lysine instead of Larginine found in the hormone derived from beef pituitaries. Variations in amino acid composition were also reported in the case of insulin from different animal sources. Determination of t h e order of amino acids in the A chain of insulin com pleted t h e sequences for this complex molecule, although its final structure re mains to be established. The structure and synthesis of thioctic acid (protogen, α-lipoic acid) was de scribed. The highest biological activity was found in 6,8-thioctic acid. T h e for mation of an amide linkage between this substance and thiamin was reported to result in the coenzyme which is required for the oxidative decarboxylation of a-keto acids. Thioctic acid was recently pro posed as a key factor in photosynthesis, light quanta converting the disulfide link
ages to free biradicals. The diastereoisomers of synthetic leucovorin were sepa rated by means of their calcium salts, and one of them was shown to be identical with the natural "citrovorum factor" as isolated from liver. Morphine Synthesis The total synthesis of morphine was described during the past year. Several new veratrum alkaloids were isolated, and structural studies were continued in this field. An abnormal steroid skeleton for jervino and veratramine, indicating a 5membered C ring and a 6-membered D ring, was reported. Phosphorylated hesperidin was claimed to be an effective oral contraceptive. An analog of sero tonin, 2-methyl-3-ethyl-5-nitroindole, was reported to prevent the vasoconstrictive action of the former when administered orally to dogs. Phenylbutazone ( sodium-4n-butyl-1,2,diphenylpyrazolidine-3,5-dione ) was in troduced into this country from Switzer land. Alone, or in conjunction with aminopyrine, it was reported to surpass the anal getic action of salicylates, gentisate, or aminopyrine in rheumatoid arthritis. Side effects were relatively high. A new anticonvulsant, 5-phenyl-5-ethylhe.\ahydropyrimidine-4,6-dione, was in troduced in Europe. In this country, the anticonvulsant action of 3-methyl-l-pentyne-3-ol and several branched chain satu rated alcohols, such as tertiary butanol and diethylcarbinol, was reported. Two
new iodinated compounds for the visuali zation of the gall bladder, 3-(3-amino2,4,6-triiodophenyl )-2-ethylpropanoic acid and α-ethyl 0- ( 2,4,6-triiodo-3-hydroxyphenyl )-propionic acid, were described. Tropine benzhydryl ether methane sulfo nate was announced as a new agent for the treatment of parkinsonism. Several new diuretic agents, which were active orally, were reported. The action of one of these, 2-acetylamino-l,3,4-thiadiazole-5-sulfonamide, "was ascribed to its high degree of specific inhibition of t h e enzyme carbonic anhydrase. The other agents described were l-propyl-3-ethyl-6aminouracil and the mercurial, 3-chloromercuri-3-methoxypropylurea. A local anesthetic, l-cyclohexylamino-2propylbenzoate hydrochloride, for topical, infiltration or spinal use was introduced. Three compounds, 2-diethylaminoethyl-a(2-cyclopenten-l-yl)-2-thienyl acetate hy drochloride, diethyl - (2 - hydroxyethyl ) methylammonium bromide-a-phenylcyclohexylglycolate, and 1 - ( 3 - hydroxy - 5methyl-4-phenylhexyl ) -1 - methylpiperidinium bromide, were proposed as anti cholinergic (antispasmodic) agents. Numerous other compounds were the subject of various investigations directed toward their use as medicinal agents. Ul timately, some of them may play an im portant role. The results described in the preceding paragraphs touch only briefly some of the many interesting investiga tions which were carried out during t h e past year.
I. E. CAMPBELL, Battelîe Memorial institute, Columbus, Ohio
M e t a l Industries . « •
Better supply-demand balance in the industry stemmed from increased production, use of substitutes, a n d improved stockpiles
.INCREASED production, use of substitutes,
fense effort and the civilian economy dur-
despite power shortages, aluminum pro-
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uted to a better balance in the metal in dustry between supply and demand, and also to the lifting of controls and restric tions on the less critical metals. Although the metals industry was still hard pressed to meet the combined demands of the de VOLUME
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the year the situation was much improved. Production of steel, aluminum, and copper, all under special control, was at a high level. The October 1952 produc tion of steel ingots reached an all-time high of just under 10 million tons, and,
JANUARY
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still in short supply during 1952, but the situation was less critical than in 1951. Decontrol of foreign copper improved the supply picture for uses which would per mit a premium price. At t h e research and development level, 49
C&EN'S ANNUAL REVIEW OF DEVELOPMENTS I N
Alumina is siphoned from tank car at a Kaiser aluminum reduction plant. T h e company's three reduction plants use over 1 billion pounds of alumina every year titanium continued to be big news, with periodic announcements of progress in both production and fabrication. Aetivities in t h e refractory-metal field assumed major importance as need for high, temper ature materials became increasingly acute. A n event of special importance during the year was the release in June of the five-volume report on "Resources for Free dom" b y the President's Materials Policy Commission. This monumental study deals with estimated requirements and supplies of materials over the next 25 years, and contains a wealth of excellent data on the economics of many metals and on techno logic trends as they pertain to future sup plies. Industry has commended the com mission for the Bne job done and for various policies recommended, but has strongly criticized numerous recommen dations, especially those concerned with multilateral contracts, international buffer stocKS, ana international uuner stoc-Ks combined with limited quota arrange ments. Molybdenum. Problems involved in the alloying, protection, and fabrication of molybdenum were all t h e subjects of ex tensive study. Several molybdenum alloys became available commercially during t h e past year, marking the first time that molybdenum base alloys have been avail able commercially. Although "protected" molybdenum was available o n order, t h e protection of molybdenum against oxida tion continued to be a major stumbling block in extending commercial applica tion of the metai in the high temperature field. Substantial progress in the welding of molybdenum renewed hope of obtaining cold ductile welds commercially.
50
Chromium. Announcement by the Bu reau of Mines of the preparation of ductile sheet chromium o n a laboratory scale and the preparation of ductile alloys contain ing up to 407c chromium gave further stimulus to attempts to produce cold duc tile chromium. With renewed interest in the metal, came additional fundamental information on its properties. A redetermination of the melting point of chromium gave a value of 1903° ±: 10° C , approximately 65° C. above the previously accepted value, and evidence of a hitherto unknown α-β trans formation at 1840° C. A Bureau of Mines report suggested the possibility of a low temperature modification to explain anom alous low temperature ductility of hy drogen-reduced chromium. Vanadium. Although ductile vanadium became available commercially in modest quantities in 1951, interest in the product failed to materialize. Despite the growing stockpile of vanadium-bearing materials, no major new uses for vanadium were publicized. Copper and Nickel. The trend of re placing copper with aluminum in many applications continued during the year and was partially responsible for improve ment in the copper situation. Domestic producers planned to invest over a third of a billion dollars in 11 new projects; many of which are expected to start pro duction in 1953. Nickel continued t o be in short supply and efforts went on to expand the available supply by improved efficiencies of recovery and use of low grade ores. Germanium. The promise shown by ger
CHEMICAL
manium as a transistor material, and im provements in techniques in the prepara tion of germanium of the special purity required for such applications, stimulated interest in the utilization of new sources of germanium. Tin. The outlook for tin was brighter in 1952. End-use restrictions were eased and it was predicted that all controls would be lifted in early 1953. The use of tin alloy coatings as substitutes for more critical materials was expanded. Atten tion was called to the usefulness of the tin-zinc coating in protection against gal vanic corrosion where components are in contact with aluminum structures. Of particular interest to chemists was the publication of a comprehensive survey of the chemistry and applications of organotin compounds. Zinc. Despite mine closings and price declines, the zinc production goal was upped to provide 1.32 million short tons in 1955. Late in the year, however, the goal was cut to provide a total supply of 1,245,000 tons in 1 9 5 6 - a reduction of 3 3 % in the amount of additional zinc called lor over the 1950 supply. Magnesium. Reactivation of six govern ment plants made it possible to more than double the 1951 production in 1952. Much of this, however, is high cost out put purchased by the Government. A large increase in the use of magnesium alloys in both ornamental and structural uses was noted in the automotive field, and increased interest was shown in mag nesium by the aircraft industries. Considerable publicity was given to use of sacrificial magnesium anodes in marine applications. Advance in methods of protecting magnesium led to claims that magnesium can be made as service able as properly protected steel or alu minum under average conditions. Aluminum. Round two of the expansion Protective coatings for molybdenum com posed of chromium and frit were tested
AND
ENGINEERING
NEWS
THE CKEMSCAL AND CHEMICAL PROCESS INDUSTRIES
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program for aluminum was well under w a y in 1952 w i t h Alcoa, Reynolds, and fCaiser adding about 415,000 tons t o their combined annual capacities. Further ex pansion o n the part of the "big three/" and the entrance of Anaconda Copper and Harvey Machine Co. as producers, is ex pected to add a n additional 200,000 tons i n 1953. A third round of expansion, expected t o add an additional 200,000 annual ton capacity b y 1953, w a s an nounced b y DPA. Olin Industries, a new comer to the aluminum production field, will participate i n the third-round expan sion. These additions d o not include Al coa's proposed Alaskan project, which, if realized, could add 800,000 tons t o the United States' annual capacity. An item of special interest was t h e pro duction of a giant aluminum ingot w e i g h i n g 3.5 tons by Kaiser Aluminum at Spo kane, Wash., for the mass production of Large, one-piece aircraft parts. The Apex Smelting Co. announced, without details, the constmction of a com mercial pilot plant in the Pacific North west to produce aluminum-silicon alloys t>y the electric furnace reduction o f alu minum-silicate clays. In the search for a lightweight mate rial with improved high temperature prop erties, special aluminum powders, con taining controlled amounts of oxides, were consolidated by powder metallurgy tech niques and then extruded as rod a n d bar stock to produce a material with high temperature tensile and creep properties, markedly superior to the best aluminum alloys previously available. Although this development is still in its infancy, it may well extend the useful temperature range o f aluminum. Titanium. As the titanium industry re doubled its efforts to get into high gear, i t was plagued with plenty in the midst o f shortages. Despite increasing demand, primarily from the armed services, pro ducers were finding it difficult to dispose of metal produced, since much of t h e metal was not all of the desired quality. Consistent production of high quality sponge, reduction of costs, and expansion of facilities were all problems of major importance to the neophyte industry a s the year ended.
VOLUME
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Aided by favorable government con tracts, D u Pont and Titanium Metals, pio neers in sponge production, were expand ing production. Newcomers were either going into production or announcing in terest at frequent intervals. At the same time, both old and potential producers were carrying out extensive and intensive searches for new processes, as evidenced by 'Du Pont's announcement that their re search expenditures o n new methods amounted to $1 million annually. Several announcements relative to new electrolytic processes appeared during the year, but electrolytic titanium w a s un available commercially and there were widespread misgivings as to the quality of the metal produced by some o f the announced processes. Zirconium and Hafnium. Carborundum Metals Co., a new organization founded for the purpose of producing zirconium and hafnium to meet both AEC and civilian needs, announced plans to pro duce sponge at a cost of $15 per pound, presumably by the Bureau of Mines proc ess. Although iodide zirconium has been available commercially for a number of years at a premium cost, zirconium sponge has not been available for general use, heretofore. Although the price o f the sponge would still be high, there w a s evi dence that it would find a ready market for specialty applications. Iron and S t e e l · In spite of the 54-day vceel strike, which cost the industry an estimated 19 million tons, total net ingot production amounted t o 93.5 million tons for 1952. This was only about 11.5 mil lion tons short of the 1951 production figure. A terrific expansion program, which amounted to 7.2 million tons of ingot capacity, and more efficient steelmaking practices helped to offset the lost pro duction. Capacifv for 1953 is estimated at 116 million as and long range fore casters predict 138 million tons by 1960. The possibility of a shutdown i n the spring of 1953, because of an iron ore shortage, faded as losses in ore shipments d u e to strikes were almost offset b y in creased lake-fleet capacity. A peak load, short o f war, was placed on the dwindling iron ore reserves of the Mesabi Range, but ores from Labrador
1 » » »JANUARY
5,
1953
and Venezuela were expected to relieve the burden placed on t h e domestic re serves. Ore supplies in Michigan were more encouraging than at any time in recent years. In addition, n e w supplies were being added by exploration' faster than existing bodies were being depleted.· Shortages and restrictions o n alloying elements continued to plague steelmakers. Nickel continued to be t h e scarcest of all alloying. elements and straight chromium steel w a s used to replace 18—8 stainless to conserve nickel. Widespread use of boron-treated steels for heat-treated prod ucts was instrumental in conserving con siderable quantities of manganese, nickel, chromium, and molybdenum. In tool steels there was a strong trend toward molybdenum high-speed steel to conserve tungsten. The tungsten shortage may be alleviated somewhat, however, by ship ments o f ores from South Korea, which are second only to those from Portugal. Direct reduction of magnetite ore con centrates, by use of the Arata process in the electric furnace, w a s proved to be commercially feasible for producing high purity iron. An average purity of 99.948% iron was obtained. Continuous casting of stainless and alloy steels, after years of development, was expected to become a commercial reality in 1953. Hot extrusion of steel by use of the Sejournet process made some head w a y during 1952, particularly i n the stain less industry. An interesting sidelight of this development was t h e successful hot extrusion of cast iron into hollow sections, showing that a brittle, nonmalleable metal c a n be extruded. Ceramic-Metal Combinations. Labo ratory and field studies of ceramic-metal combinations continued. Nickel-bonded chromium carbide was added to ceramicmetal bodies, which already included chromium-bonded alumina and nickel- or cobalt-bonded titanium carbide. All have good resistance to oxidation and high strength at temperatures in t h e range of 1800° t o 2100° F. L o w resistance to u^ermal shock has hampered considerably t h e successful commercial use of these materials, however, and Saws in fabri cated structures have caused difficulties in development-type applications.
51
