RESEARCH Select α Reducing Agent That Can Attack One Functional Group, Leave Another Alone . . . For example, to reduce on ester in the presence of a corboxylic acid group, ose a combination of sodium borohydride and lithium bromide NaBH 4 Aldehydes Ketones Acid chlorides Esters Acids Salts Nitriles Nitro compounds
++ ++ ++ — — — — —
NaBH 4 +A1C13
NaBH 4 -hLiBr
++ ++ ++ ++ ++ — +—+
++ ++ ++ + — — —. —
B2He
LiAlflU
LiAlH (OMe)3
LiAlH (0-f-Bu) : ,
++ ++ —
++ ++ ++ ++ ++ ++ ++
++ ++ ++ ++ ++ n. a. ++ 4-
-h+
+
++ — ++ —
+
At 2 5 e - 7 5 ° C : + + Reacts rapidly -f- Reacts at moderate rate — Reacts quite slowly or negligibly
Versatile Hydroborons They tailor reduction reactions, also lead t o organoboranes and primary alcohols quickly llvER since the Manhattan Project, hydroborons have slowly changed from lab curiosities to industrial chemicals. And some of the newest research at Purdue University could speed up the trend. Here's the latest on what they can do: • Act as selective reducing agents • React with primary terminal olefins to make trialkyl organoboranes • Make alcohols from an olefin mix tures That borohydrides are good reduc ing agents has been known for some time. N o w , Herbert C. Brown and coworkers at Purdue's chemistry de partment have found they can increase the mild reducing power of sodium borohydride with lithium bromide or aluminum chloride. They've also found they can lower the very power ful reducing potential of lithium alu minum hydride by adding alkoxy groups. These changes gave a series of reducing agents that can reduce groups selectively. Since the reducing agents can b e varied at will from mild to extremely 28
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active from basic to acidic, you can choose your reagent to get the reduction you want. Thus, a func tional group like an ester can be re duced in the presence of a nitrile group, or the nitrile group in the presence of an ester. Similarly, a carboxylic acid group can b e reduced in the presence of an ester, or die latter can be reduced preferentially. Many other selective reductions are possible, says Brown. Sodium borohydride was discovered by H. I. Schlesinger, Brown, and co workers at the University of Chicago during World War II. But declassifi cation problems held u p publication and commercialization. Consequently, lithium aluminum hydride, although discovered later, became commercially available sooner and has received the major attention for organic reductions. "The versatility of sodium borohydrides for such reductions is only now becom ing apparent", says Brown. The drug industry is making use of these selective reducing agents. Brown's research has been assisted b y grants from Upjohn, Parke-Davis, and Merck. • Sidelights Look Good Too.
While
-I-+ 4-+ n. a.
— --
studying the NaBH 4 -AlCl 8 combina tion, Brown and B. C. Subba Rao came up with a new method of making trialkylboranes from simple olefins. As examples, ethylene, 1- and 2-pentene, diisobutylene, cyclohexene, and styrene form their respective trialkylboranes in 90% yields. These organoboranes can be oxidized to alcohols. So, says Brown, styrene and diisobutylene readily g i v e their cor responding primary alcohols. The re action provides a simple procedure for the hydration of olefins in an anti-Markownikoff direction, opposite to that achieved in acid catalyzed hydration. A number of functional groups can be on the olefin. Because of this, says Brown, the pharmaceutical industry may be able to synthesize new boron drugs containing these functional groups. Boron compounds may be use ful in brain tumor treatment (C&EN, April 23, 1956, p a g e 1 9 4 4 ) . When boron reacts with a neutron, it releases an alpha particle that can kill a ceil at its point of origin in a tumor. Oxidizing the organoboranes to alco hols may be a useful w a y of making oxo-type alcohols (C&EN, March 18. page 1 6 ) . But t h e catch here is the present cost of these reagents, says Brown. But with the intensive research effort n o w being devoted to boron chemistry, cost may not always remain a major hurdle. •
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• Lower Ash Content than any filter paper we have tested —less than 0.007% for quantitative grades. 9 Higher Alpha Cellulose Con tent than any filter paper we have tested—97-98% for quantitative and qualitative grades. 9 ISo Price Premium. Your company purchasing agent pays no more for the finest. For the chemist who can specify his brand of filter papers, S & S Analyti cal Filter Papers offer outstanding advantages. These advantages are possible because of the skill, care and quality control methods used by S & S from selection of raws through to the finished product. Every Lot Pre-testefl A substantial test portion of each batch of S & S Analytical Filter Papers is used for quality control determinations in our laboratories. This helps assure that you receive fil ter papers uniform physically and chemically—lot after lot, month after month, year after year. Specify S&S Analytical Filter Papers for extra advantages to you in your work at no extra cost. Get the "mar gin of safety'* in your analyses that comes with using what many chem ists believe to be the finest analytical filter paper in the world. FREE S A M P L E R ry~.Z'~ ù i4ir*" *' \, " '\ /issv J»»»*1* . (jgj) s ! U n ^ j
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30
C&EN
MAY
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1957
RESEARCH
Labs & Institutes Nonprofit research institutes originally set up to do basic research have changed so they are now applied business institutions, says Lewis E. Harris, chairman of the American Council of Independent Laboratories' committee on legislation and tax favored competition. "We oppose those outright commercial business enterprises which are camouflaged as so-called institutional and educational organizations and which use such guise to evade taxation. . . . These are grossly unfair, and they deprive our Government of large sums of tax funds." Harris cites the National Science Foundation's report on research and development by nonprofit research institutes and commercial laboratories (C&EN, Oct. 15, 1956, page 5O02). The report said that 12 nonprofit institutes did $53 million worth of research and development in 1953, 6% of which was devoted to basic research. By devoting too much attention t o applied research, the nonprofit institutes and universities undermine the very basis of scientific knowledge, Harris declares. "The nonprofit institutes have very wide publicity, and they attract customers who are influenced by the boards of trustees. These people have been led to believe they are doing something fine for the community, but usually, not only does the business change, but at the same time the nonprofit institutes can depreciate and they can charge off all equipment costs immediately within the year in which they are operating. It is very fine thing to end up and show no profit. They use what we term 'profit' to expand and grow larger and larger to provide more services and freeze out other types of business." • Universities, Too. Although the NSF survey did not cover research centers and the like at universities, Harris believes there is no difference. They, too, are a multimillion dollar business. "The pressure within the universities for business research has tended to overshadow the primary function of the teaching process. We can ill afford to weaken our standards of effective teaching to make way for additional business research within university halls." Harris says that universities in many instances delay publication of research results until the industrial sponsor has the product on the market. He asks if this is basic research for the public good. H e recommends legislation requiring "so-called nonprofit research institutes, university research laborato-
ries, and all others operating as tax exempt or tax favored, to publish all research results immediately for the public good/' Harris made his remarks before a Washington, D . C , meeting of ACIL.
Correcting Chlorosis The ferric chelate of ethylenediaminetetraacetic acid (EDTA) is widely used for treating iron chlorosis in plants. However, it has a drawback: It will not correct diis mineral deficiency in plants grown on certain soils, particularly alkaline ones. Now researchers at Geigy Chemical have synthesized a phenolic analog of EDTA; they say it corrects iron deficiencies in a variety of crops grown on the alkaline, clay soils of the western U. S. The compound is the ferric chelate of ethylenediamine di-(o-hydroxyphenylacetic acid). According to H. Kroll (now at Olin Mathieson), Martin Knell, James A. Powers, and John V. Simonian, the compound is: • Effective in small quantities even on extremely alkaline soils. • Not adsorbed on clay. •Apparently not affected by soil microorganisms. • Relatively nontoxic even in large doses. To date, the compound, known as Chel 138, has been produced only in limited quantities because production costs are high. Geigy is working on a pilot plant process for the chemical and hopes to overcome the high cost soon to make Chel 138 available in commercial quantities. In April 2 0 JACS, the researchers say they synthesize the compound by adding two moles of hydrogen cyanide to the Schiff base from salicylaldehyde and ethylenediamine; the dinitrile obtained is hydrolyzed to Chel 138. As an aside to their main purpose, the researchers find that ethylenediamine di-(o-hydroxyphenylacetic acid) is a sensitive analytical reagent for ferric iron.
ί A vaccine that protects 80% of vac cinated mice against leukemia has been developed at Sloan-Kettering Institute; the vaccine does not protect the mice against other forms of cancer. Char lotte Friend prepares the vaccine by killing with formaldehyde a leukemia virus said to be the only one that con sistently causes mouse leukemia even in adults. She told the Chicago meet ing of the American Association for
In every grade, he maintains an "A+" (Methocel is his subject, quality control his method) Of the various tests to which Dow quality control men subject Methocel®, a most important one involves a tube. T h e answers it gives assure complete uniformity of this D o w methyleellulose. As Methocel is being processed, our technicians run batch samples through a capillary-type tube of the Ubbeholde Viscometer. Too fast? Too slow? (Too thick or thin?) Rate of flow through the tube provides a simple-but-exaeting test. And every Methocel grade (of which there are three in nine viscosities) must pass "Summa Cum Laude".
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Of course, consistency is an inherent advantage of Methocel, for it's a synthetic gum. Thus, by exercising the proper controls and techniques in production, quality never varies. Result: I n all types of products—from paint to shampoo— Methocel offers an unusual degree of viscosity control. It's simple methods like this, along with those more complicated, that help make your chemical dollar worth more now and in t h e future . . . that assure you the same qualitv
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1957 C & E N
31
RESEARCH
C a n c e r Research t h a t this is t h e first successful vaccination against cancer in mammals.
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• A n e w m e m b r a n e which is permea b l e almost exclusively t o certain ions in t h e presence of other ions of t h e s a m e charge has been prepared b \ H a r r y P. Gregor a n d Harold Schonh o r n of Brooklyn Poly ( M a r c h 2 0 JACS). These membranes a r e multilayers of barium stéarate w h e r e t h e potential-determining ion is transported transverse to t h e axis of orientation. According to t h e scientists, t h e multilayer m e m b r a n e electrodes can b e used t o measure activities of ions in mixed electrolytes. They are reversible to b a r i u m ions even in t h e presence of h i g h concentrations of sodium ions. Biochemical problems can also b e attacked—such as determining calcium i o n activities, t h e so-called " u n b o u n d " calcium concentration, in blood a n d other biological fluids. • Growth-promoting proteins occur in tissues a n d organs of adult chickens as well as in embryos, Morgan Harris a n d R o m a n J. Kutsky of University of California say. Some agent m a y inhibit these proteins after t h e animal reaches maturity, they believe. • A tasteless ester o f chloramphenicol
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32
C&EN
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h a s been synthesized b y t h e German firm of C . F . Boehringer & Soehne, Mannheim-Waldhof. T h e molecule carries a primary a n d a secondary alcohol group esterified with h i g h e r fatty acids. T h e s e esters are practically insoluble in water a n d therefore tasteless. Of t h e esters tested, chloramphenicolmonostearoylglycolate proved t h e most suitable. T h e conventional form is bitter a n d therefore generally used as capsules or coated pills. F o r main purposes, however, a liquid form would b e more suitable. • A lotion for poison ivy has been d e veloped b y Ciba. I t consists of Pyribenzamine, said t o relieve itching a n d burning, a n d zirconium oxide, said to speed healing by inactivating t h e poison. Ciba says t h e lotion, called A n t ivy, not only relieves t h e discomfort of ivy poisoning, but also can prevent most cases if applied in advance. • Halotestin, Upjohn's orally effective androgenic-anabolic steroid, is n o w available to t h e medical profession (C&EN, April 30, 1956, p a g e 2 1 3 4 ) . • Denver Research Institute's contract research rose 14% from t h e preceding year t o $1.3 million for t h e year ending J u n e 1956. D R I worked on 6 1 industrial projects, 3 4 government, a n d five basic research projects sponsored b y t h e university.
