New Pteridine Synthesis - C&EN Global Enterprise (ACS Publications)

Method features variable construction of pyrimidine ring, with advantages of conventional methods retained. Chem. Eng. News ... First Page Image. LOND...
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INTERNATIONAL action may take place. I n the apparatus described, a beam of accelerated molecules is directed into a localized region of space w h e r e it collides with a stream of other molecules. Bull explained that some preliminary experiments have been done in which they formed CsCl b y the impact of CC14 on Cs. T h e rotor method has the disadvantage that it is suitable for comparatively heavy molecules only, said Bull, b u t it has the advantage of providing a relatively high intensity. The flux of

neutral molecules through the collision region was the equivalent of several micro-amps of singly charged ions. American Contribution. T h e Faraday discussion was well attended b y the contingent of American chemists now in Europe. Of the 27 papers presented, 12 were from American laboratories. Over 225 people w e r e present for the conference, which included an exhibit of apparatus used in the Birmingham laboratories, as well as apparatus displayed by visitors to the conference.

N e w Pteridine Synthesis Method features variable construction of pyrimidine ring, with advantages of conventional methods retained LONDON.—A new approach to pteridine synthesis makes it possible to construct the pyrimidine ring in a varied manner, E. C. Taylor, Jr., told the Symposium on the Chemistry and Biology of Pteridines held here recently under the sponsorship of Ciba Foundation. Taylor says the synthesis retains advantages of conventional methods with regard to ease of placing substituents on the pyrazine ring. The method, developed by Taylor and his coworkers at the University of Illinois department of organic chemistry, involves preliminary synthesis of 2,4(1/7, 3H)-pteridinedione (lumazine) or 4 ( 3 H ) - p t e r i d i n o n e b y a conventional procedure. Next step is ring cleavage of the pteridine, usually b y aminolysis, to an N-substituted 3-aminopyrazinamide or its derivative. Finally, ring reclosure of the pyrazine to the desired pteridine is carried out by any of several methods. In a review of opening reactions of pteridines, Taylor emphasized the importance of these cleavage reactions in elucidating the structure of pteridines. The in vivo utilization of pteridines may also involve ring opening reactions. Possible transformation of pteridines into other heterocyclic systems such as the purines, must involve cleavage of the pteridine ring system, Taylor maintains. Alkylation Studies. Alkylation of some simple hydroxypteridines by H . C. S. Wood, Royal Technical College, Glasgow, shows that the products generally are iV-alkylpteridones. Constitution of the compounds was determined by degradation to pyrazine derivatives, followed by unambiguous synthesis of the pteridone. On treatment with methyl sulfate, 4hydroxypteridine gives a mixture of 31776

methyl-4-pteridone and 2-methylaminopyrazine-3-carboxyamide, Wood says. T h e related l-methyl-4-pteridone was also synthesized. Other compounds methylated were 4-hydroxypteridine, 7-hydroxypteridine, lumazine, 2-hydroxypteridine, and 6-hydroxypteridine. N o alkyl derivative was found in either of the latter two studies, Wood notes. These alkylated pteridines underwent ring fission with great ease, Wood says, and this technique may b e helpful in elucidating the structures of naturallyoccurring pteridines which are normally resistant to degradation. Pteridine Ring System. Studies on the fundamental chemistry of the pteridine ring system, carried out at Australian National University, have resulted in the synthesis of some 40 monosubstituted pteridines, according to D. J. Brown. T h e most recent successful substitutions include: the methyl group at position 2; the methyl, methylthio, and hydrazino groups at position 4; and t h e amino, dimethylamino, mercapto, methylthio, chloro, and methyl groups at position 7. These and earlier monosubstituted pteridines fall naturally into two classes. Brown says. T h e first group is composed of those which have hydrogen bonding groups. These compounds are soluble only in boiling water, have high melting or decomposition points, and are stable. Second class has groups which do not cause intermolecular bonding. Members of this group are often soluble in cold water and are appreciably soluble in all organic solvents. Furthermore, they have melting points below 200° and are relatively unstable to reagents and to p H changes. Pteridine Synthesis. Another synthetic approach to formation of compounds containing the pteridine nucleus CHEMICAL

and to preparation of related compounds involves o-aminonitroso compounds. Reactions of these derivatives of the benzene, naphthalene, pyridine, and pyrimidine series have been used successfully in such syntheses, says G. M. Timmis, Chester Beatty Research Institute, London. Products include triaza, tetraaza, and pentaaza benzanthracenes and dibenzanthracenes, pyrazolopteridines, 7aminopteridines, pyridopyrazines, pyridoiminazoles, pyrimidothiadiazoles, a n d quinoxalines. In all cases the structures are determined by t h e m e t h o d of synthesis, Timmis notes. Pteridine Derivatives. Some 8-substituted pteridine derivatives, synthesized by Gertude B. Elion of Wellcome Research Laboratories, m a y b e regarded as simple analogs of the purine nucleosides or of riboflavin. Interest in Miss Elion's work was stimulated b y work carried out by H. S. Forrest, Caltech. Forrest has successfully isolated a yellow pigment from the eyes of a m u tant of the fruit fly, Drosophila melanogaster. Preliminary experiments on structure of this compound indicate t h a t it contains a pteridine nucleus with a lactyl group attached, probably at Ne, Forrest believes. Considerable discussion took place concerning the relationship of color to constitution in this type of compound. It was thought that the yellow pigment is probably a precursor of the red pigment found in the wild-type flies, a n d the suggestion was m a d e that the latter might be a pteridinium salt.

Rich Uranium O r e Found in A u s t r a l i a Pitchblende recently found near Adelaide, Australia, is said by mining experts to be the first discovery on that continent of the richest form of uranium ore. L u m p s of ore are reported to contain 70% or more of uranium oxide. Advantage of the ore is in t h e readiness with which it can b e refined to uranium oxide, a n d possibly some of the ore may be exported without refining. A large refinery is under construction at Port Pirie, South Australia, to handle the ore from another established state field at Uranium Hill. Russians Tell of N e w Caustic Soda Process A new method of producing caustic soda is described in Doklady AN (Trans. Acad. Sci. USSR). V. M. Kakabadze and T . A. Ivanova use sodium sulfate reduced to sulfide at 850° to 1000° C. with a high MnO2 ore. AND

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INTERNATIONAL Optimum temperature subsequently is 18° to 25° C , a n d best ratio of N a 2 S / M n 0 2 is 1:1.5. T h e reaction is Na2S + M n 0 2 + H 2 0 = 2 N a O H + MnO + S In t h e process of desulfurizing Na 2 S concentration is important, a n d in the experiments r a n g e d from 5 to 15.5%. O p t i m u m was found to be 11.5 to 1 2 % . Desulfurizing takes about t w o hours. T h e M n 0 2 or other manganese ore should b e finely powdered (400 m e s h / c m 2 ) . T h e resulting caustic solution has a concentration of about 117 to 120 grams per liter. OEEC Plans Productivity

shares, with a further 40% divided equally among Socony-Vacuurn, Standard Oil ( N . J . ) , Standard of California, Texas Co., a n d Gulf Oil. R e maining 2 0 % would b e shared between Royal D u t c h Shell a n d France's Compagnie Française d e s Pétroles. N o r w a y ' s Research Bill About 0 . 2 5 % of Norway's gross national income is at present spent on research projects annually, or between $7 and $8 million. These figures were revealed b y Robert Major, director of the Norwegian Technical Research

C&EN Foreign Correspondent Contributing to This Issue: W. G. CASS, Russia

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Organisation for European Economic Co-operation has published a summary of t h e program scheduled for t h e European Productivity Agency which was set u p b y t h e O E E C council last May. Included in the six main sections of t h e program is o n e on applied research a n d technology. Aim of t h e productivity campaign is t o increase production through better methods, equipment, a n d in general b y avoidance of waste of time, money, materials, space, or h u m a n effort. Final purpose is achievement of a higher standard of living in E u r o p e . Working within t h e general framework of O E E C and in conjunction with its technical committees a n d other bodies, E P A will assist National Productivity Centers in t h e 18 member countries in collating, acquiring, and disseminating or exchanging knowledge. In t h e field of applied research and technology, t h e agency will facilitate contacts for exchange of information and views between those in charge of organizing and administering research, through congresses or symposia, and especially b y appointment of a scientific liaison officer. Improvement of existing channels of technological dissemination in industrial circles will b e an essential task of t h e agency.

Α. Η. Τ. CO. ASSORTMENT OF

Polyethylene LABORATORY

A t o u g h , flexible, paraffinic thermoplastic o f translucent white a p p e a r a n c e with w a x like surface which c a n b e m a r k e d with the usual glass marking pencil. Lightweight (specific g r a v i t y 0 . 9 2 ) , a n d u n b r e a k a b l e in normal use. Highly resistant t o chemical attack. Polyethylene, o f high molecular weight, is used in l a b o r a t o r y w a r e a n d has a softening r a n g e o f a p p r o x i m a t e l y 1 0 8 ° t o 11 1 ° C . Since both strength a n d chemical resistance a r e decreased a t e l e v a t e d temperatures, articles o f this m a t e r i a l a r e used most satisfactorily a t t e m p e r a t u r e s below 5 5 ° C a n d are not r e c o m m e n d e d f o r use a b o v e 7 0 ° C .

I r a n O i l t o G o Back Into Production Eight Western oil companies have agreed on t h e terms for setting u p a multimillion-dollar combine to p u t Iranian oil back on t h e world market. Combine includes t h e Anglo-Iranian Oil Co. as major partner. Official sources have said that a flexible plan has been worked out among t h e companies for reviving t h e Anglo-Iranian works a n d jointly selling t h e output. Tentative agreement provided for Anglo-Iranian t o get about 4 0 % of t h e V O L U M E

Council. This is about a third as much, proportionate to gross national income, as is spent by the U . S. A. on scientific and industrial research. T h e r e are about 1000 research workers i n public a n d private laboratories, and 11 n e w research institutes have been established since t h e war, including Central Institute for Industrial Research. They will occupy t h e center being built at Oslo.

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Polyethylene is suitable f o r use at r o o m t e m p e r a t u r e s in contact with liquids such as distilled water, mercury, buffer solutions,

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concentrated alkali, concentrated hydrofluoric, phosphoric, hydrochloric a n d acetic acids, sulfuric acid to 6 0 % , chromic acid t o 4 0 % , dilute nitric a c i d , fluoboric acid t o 4 5 % , formic acid t o 9 0 % , f o r m a l d e h y d e t o 3 6 % , hydrogen p e r o x i d e , ethylene glycol and glycerine. Prolonged storage in p o l y ethylene bottles o f certain volatile r e a g e n t s such a s acetone, ether, t o l u e n e , etc., is not recommended because o f their relatively high rate o f permeation through the walls. This limitation does not affect t h e use o f such materials in o p e n polyethylene vessels such a s b e a k e r s , funnels, etc., although some o f these reagents m a y cause slight swelling o f t h e plastic. Polyethylene w a r e should n o t be used with bromine, carbon bisulfide o r concentrated nitric a c i d .

Copy o f Bulletin 114, listing complete assortment now available, sent upon request.

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ARTHUR H. THOMAS COMPANY Laboratory Apparatus and Reagents

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