Potential Raw Materials for Cortisone Offer Abundant Supply - C&EN

Nov 5, 2010 - In this connection, he noted that in the case of an infection such as pneumonia, the interaction of invading pneumocci with cell tissue ...
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THE CHEMICAL WORLD THIS WEEK organic sulfides, nitrogen bases, naphthalenic acids, and phenolics. In general, refiners a r e recovering waste gases or burning them with a minimum of pollution. Gas leaks go to flares which are designed to reduce smoke emission with some making use of a water spray. Collection systems limit t h e problem of dust arising from catalyst regenerators or cracking units, while hydrocarbon gases are not considered a source of pollution. Phosphorus Plant Effluents In order to avoid smoking of manholes caused by the presence of phosphorus which has been discharged to city mains, M. L. Parker of Oldbury Electrochemical Co. described a solution which involved chlorination of the effluents. Subséquent hydrolysis forms the weak acid which eliminates the fume problem. Legal and regulatory aspects of the pollution problem were reviewed by four speakers. Charles Maddock, Hercules Powder Co., noted t h e similarity in the preambles of several bills which have established state or local commissions. In most eases, the legislators have declared it their purpose to abate the menace to public health, to provide for the relief of waters from pollution, etc. These commissions have been organized to establish or implement control of pollution, to cooperate with federal and other agencies, to conduct studies of pollution nuisances, to promulgate rules and regulations, and to issue permits. Maddock concluded that he had observed a trend toward approaching t h e pollution matter from a longrange view, a procedure which was productive or some very good legislation. In this he was seconded by T. S. O'Brien of Air Reduction Co. who noted that specific standards of pollution were determined only after public hearings before commissions and that two state water pollution control boards were established with the authority to promulgate standards of water purity. T h e prediction t h a t many more cases of air pollution were likely to reach the courts within the next few years was made by F. L. Seamans, Aluminum Co. of America. He emphasized that investigation of claims against a company in a fume case involves a mass of data, a battle of the experts representing t h e claimants and the défendent, and most important, a simple yet effective presentation of the data to a layman judge or nontechnically trained jury. Consequently, h e proposed that in order to do justice to the type of evidence gathered, cases should be judged by a board of experts who have a scientific background. Community Relations Aspects T h e correction of stream pollution of the South River, below Waynesboro, Va., was cited by Roy McCracken of the Du Pont Co. as a joint venture of t h e town of Waynesboro, three major industries

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located in the town, and representatives of the Virginia State Water Control Board. As a result, there has been established a feeling of cooperation and trust among the different groups. Looking at the Du Pont plant waste disposal, McCracken observed that during the past few years, the B.O.D. flowing load on the river has gone down considerably, while the dissolved oxygen has increased. Elimination ot waste at the source was accomplished at the Waynesboro acetate rayon plant by such process improvements as the elimination of the production of acetic anhydride and purchasing the material instead; better control of acid losses, and use of more modern, efficient acid recovery equipment; and reduction of acetone losses through the air conditioning eciuipment. In all, waste products are reduced to one fourth the previous level at an expenditure of $500,000 b u t with considerable savings. T h e Kanawha Valley story, the subject of another interesting case history in community relations, was outlined by M. C. E. Hamilton, Jr., of Union Carbide and Carbon Corp., Adverse reaction on the part of the1 public and press to a West Virginia State Health Department report which indicated a considerable amount of particle settling from the atmosphere, as much as 1400 tons per square mile per year, almost culminated in unfavorable and hasty legislative action. However, the turning point was reached upon publication of a series of 32 articles in a local

newspaper. This material told of economic and physical difficulties encountered by industry in combatting pollution, a n d served to "clear the air" by getting t h e facts to the public. With the first step in community cooperation accomplished, the formation of a citizens committee to pursue an a b a t e ment program with the assistance of t h e state health department and industry followed quite naturally. Meanwhile, industry had intensified measures to control pollution, such measures including t h e replacement of incinerators, abatement of fly ash from steam plants, process changes to limit flume emissions, the substitution by the railroads of diesels for coal-burning locomotives, and the like. Interstate Compact Discussed T h e solution of pollution problems in the Ohio Valley has taken a long stride forward with the formation of an interstate compact composed of eight states ( Illinois, Indiana, Kentucky, New York, Ohio, Pennsylvania, Virginia, and W e s t Virginia ). Speaking at the dinner meeting, E d w a r d J. Cleary, executive director and chief engineer, Ohio River Valley Sanitation Commission, said that the formation of the commission has provided a mechanism for an integration of effort on t h e part of stato regulatory agencies, the Federal Government, industries, municipalities, and the people of the Ohio River Valley to solve a common problem.

Potential Raw Materials for Cortisone Offer Abundant Supply C&EN REPORTS: A C S N o r t h Jersey Section, Baekeland A w a r d M e e t i n g

NEWARK.—Potential, commercial sources of raw materials from which adrenal hormones, and especially cortisone, may h,M. produced will in the not too distant future provide abundant quantities of cortisone, declared Lewis II. Sarett, recipient of the 1951 Leo Ilendrik Baekeland Award of the North Jersey Section for his synthesis of cortisone. The biennial award, which commemorates the technical and industrial achievements of Baekeland and encourages younger chemists to emulate his example, is sponsored by Bakélite Co. and consists of a gold medal and $1000. While devoting the major portion of his address to a review of research and botannical effort in attempts to locate steroidcontaining plants and to various cortisone syntheses attempted, the medalist also referred to the value of cortisone to the future of theoretical medicine. In this connection, he noted that in the case of an infection such as pneumonia, the interaction of invading pneuniocci with cell tissue of the lungs disappears upon treatment with A C T H or cortisone. However,

CHEMICAL

examination of t h e cell tissue reveals t h e presence of just as many pneuniocci as before the hormone treatment. But medicine is thereby offered the opportunity of observing the disease without sickness, Sarett said in quoting a statement by Peter II. Forsham of the Harvard University Medical School. In dealing with the potential d e m a n d for cortisone vs. the supply of bile acid, the present starting material, Sarett came to the conclusion that the present process does not meet medical requirements, nor will it be able to do so in the future. He then turned to alternative starting materials which may hold more promising potential for the future. Sarmentogenin Sarmentogenin has been found in small amounts in some of the 3 3 species of the African vine, Strophanthus. Original research work had indicated t h e presence of sarmentogenin in one species of this plant, but subsequently this species was lost in what developed into a peculiar

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PERKIN-ELM£R

INSTRUMENT DIGEST A c o n d e n s a t i o n of some of the a r t i c l e s a p p e a r i n g i n the Spring issue of THE PERKIN-ELMER INSTRUMENT NEWS, a q u a r t e r l y p u b l i c a t i o n of The PerkinElmer C o r p o r a t i o n , manufacturers of scientific instruments-lnfrarec3 Spec­ t r o m e t e r s , Tiselius Electrophoresis A p p a r a t u s , U n i v e r s a l Mon o c h r o m a tor,

Norwalk, C o n n .

Flame P h o t o m e t e r s , Continuous I n f r a r e d A n a l y z e r , Low-Level A m p l i f i e r s - a s w e l l as A s t r o n o m i c a l E q u i p m e n t , Replica G r a t i n g s , T h e r m o c o u p l e s , Photo­ g r a p h i c Lenses, C r y s t a l O p t i c s , a n d S p e c i a l Instruments for the Government. For f u r t h e r i n f o r m a t i o n , w r i t e The P e r k i n - E l m e r C o r p . , N o r w a l k , C o n n .

April, 195!

DENSITOMETER SIMPLIFIES QUANTITATIVE ANALYSES T h e new densitometer attachment for Model 12-C Infrared Spectrometers makes quantitative determinations in either transmittance (per cent transmission) or ab"sorbance (optical density) readily obtain­ able. The densitometer is designed to give overall accuracies of z+z.25% in transmit· tance operation.

Vol. 2, No. 8

You c a n r e c e i v e the c o m p l e t e p u b l i c a t i o n from w h i c h * these a r t i c l e s w e r e d i g e s t e d . Write The Jerkin-Elmer Corporation, Dept. CEN, Main Advenue (Route 7 ) , Norwalk, Conn., and you w i l l receive regularly THE PERKINELMER INSrRUMENT NEWS, an 8-page quar­ terly d e v o t e d to news of t h e latest advances in electro-optical instrumentation. Here are some o f the features of current issues: INFRARED MICROSPECTROSCOPY Article by EÊkan R. Blout CHANGES IK THE MODEL 21 Double-beam Spectrophotometer Improved

page 1 page 1

HORIZON-TO-HORIZON CAMERA Panoramic Design for Air Force pages 4-5 PRESENTING PURE COMPOUND SPECTRA Staff E d i t o r i a l page 2

of this type ti ave been made, t h e difficulties in the interpretation of such a r e still great. Of particular- interest is the possibility of locating such, groups as Ο—Η and Ν—Η in the unit cell of crystalline material, since these groups are especially difficult to de­ termine by x.-ray methods. Digest of arz. article by Elkan R. Ρ ο Jaroià Corporation.

Blout,

DESIGN CHANGES IMPROVE IMODEL 2 1 DOUBLE-BEAM SPECTROPHOTOMETER T h e attachment consists of a panel and its parts directly connected to t h e Model 81 Amplifier, all mounted in t h e Model 12-C cabinet.

INFRARED APPLIED TO MICROSPECTROSCOPY Infrared microspectroscopy promises to be an increasingly useful m e t h o d for the characterization and identification of small amounts of material. T h e functions of an infrared micro­ scope are to provide an enlarged image of the specimen so that sample volume and sample weight may be reduced. Infrared microscopes have been con­ structed with which it has been possible to obtain useful infrared data on samples having weights in the range of 5 χ 1CH5 to 5 χ 10~7 grams. It is expected that with further refinements sample weights may be reduced still further. One of the most intriguing applications in which an infrared microspectrometer can be used is the determination of polar­ ization spectra of fibers and microcrystals. Although several spectro-determinations VOLUME

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Several dersign changes in the Model 21 Double-beam Infrared Spectrophotometer o v e r the past year have been aimed toward meeting suggestions forwarded from the field. Basically, these changes incorporate stronger mounting and b e t t e r adjustment access. Prism interchange is now easily made by means of a sub-table h o l d i n g the prism, Littrow m i r r o r , and accessory cams. Prisms c a n be interchanged without the necessity of recalibration. Earlier Model 21 instruments c a n b e adapted t o this improved mounting. Other changes include elimination of t h e field lents, and a u t o m a t i c placing of t h e grating filter in the optical path at a scheduled point for t h e reduction of strong light. Λη a u t o m a t i c scale c h a n g e r with 4:1 speed ratio ha.as been designed to scan high frequency regions at four times the speed of the lower regions. T h e scale is changed at the same r a t i o . With t h e s e changes, t h e Model 21 has reached a stage where it can b e considered a standard instrument. N e w changes and accessories will be added a s t h e need arises. APRIL

3 C,

1951

PERKIN-ELMER PLAN FOR RECORDING PURE COMPOUND SPECTRA Before punch card systems can be adopted for filing of pure compound infra­ red spectra, a uniform system for presenta­ tion of spectra must be decided upon. Perkin-Elmer has given the matter much thought and in the Spring 1951 issue of I N S T R U M E N T N E W S presents its ideas on the problem. T h e guiding principle is to record a maximum of information with a minimum of space and effort, and to pro­ vide enough information to be valid and sufficient for a number of years. Highlights of the system are listed below: 1—Present pure c o m p o u n d spectra with three prisms: CaF.„ NaCl, and KBr, in the range from 90ÔO cm-* (1.1/0 to 400 cm-» (25μ). 2—Different wave number scales on the abscissa will minimize waste of empty spectral space. Ordinates shall be recorded linearly in transmittance increasing up­ ward (downward?), but on paper marked in absorbance rulings. 3—Resolution should be of the order of 2-2.5 times the Rayleigh limit of 15 cm of prism base. 4—Speed of recording should be suffi­ ciently slow to permit accurate following and peak-to-peak noise less than 0 . 5 % . 5—Spectra shall be presented on paper 76 cm long by 25.4 cm high. One piece shall present the NaCl and KBr spectra, other pieces the C a F 2 spectrum, all with vary­ ing scales for different wavelengths. Perkin-Elmer is anxious for comments and suggestions from workers in the field w h o are interested in this problem. In this way, uniformity can be assured, and we can design special wavelength cams to fit the final adapted specifications.

Model 21

Spectrophotometer

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THE C H E M I C A L W O R L D THIS WEEK have and lems fered

a t t e m p t e d to p e r f o r m this a d d i t i o n , indicated that stereochemical prob­ (sheltered groups and others) inter­ with many of these approaches.

Tolal

G. L . R o y e r , c h a i r m a n of t h e N o r t h J e r s e y S e c t i o n , p r e s e n t s t h e B a e k e l a n d A w a r d to L e w i s H. Sarett, Merck & C o . , w h i l e G e o r g e B a e k e l a n d , B a k é l i t e C o . , stands by to present the $ 1 0 0 0 c h e c k w h i c h g o e s w i t h t h e a w a r d botanical riddle. A n u m b e r of e x p e d i t i o n s w e r e s e n t to A f r i c a t o find w h i c h s p e c i e s of Struphanthus produced the best y i e l d of s a r m e n t o g e n i n , a l i k e l y m a t e r i a l for t h e c o r t i s o n e s y n t h e s i s , a c c o r d i n g t o t h e s p e a k e r . O n l y 1 5 s p e c i e s h a v e so f a r been thoroughly investigated, and yields of 0 . 1 t o 0 . 2 ' γ h a v e b e e n o b t a i n e d f r o m sarmentosus. petersiatitts. ctwrmontii, gerrardiy a n d a f e w o t h e r s . H o w e v e r , a n o t h e r species tentatively identified as M P D - 5 0 h a s p r o d u c e d a 0 . 4 ' ν y i e l d of s a r m e n t o ­ g e n i n a n d is t h o u g h t to b e t h e o r i g i n a l s p e c i e s w h i c h w a s l o s t . In a d d i t i o n to t h e o i A t n c a n s p e c i e s , S a r e t t said t h a t t h e r e w e r e a b o u t 12 m o r e Struphanthus species in v a r i o u s p a r t s of t h e w o r l d . T h e fact t h a t t h e African e x p e d i t i o n s h a d provided some clues w h i c h may lead t o t h e s o l u t i o n of t h e b o t a n i c a l p u z z l e w a s h e l d to be h i g h l y significant, a c c o r d ­ i n g to S a r e t t . S a r m e n t o g e n i n is a p r o m i s ­ i n g s t a r t i n g m a t e r i a l for t h e cortisone s y n ­ t h e s i s b e c a u s e of t h e p r e s e n c e of o x y g e n in the carbon-11 position. T h e medalist t h e n i n d i c a t e d t h a t t h e s y n t h e s i s of c o r t i s o n e from this starting material would b e simi­ l a r to t h e s y n t h e s i s of d e s o x y c o r t i c o s t e r o n e starting with periplogenin. Sapogenins A n o t h e r c l a s s of s t e r o i d s w h i c h h a v e s o m e p r o m i s e as s t a r t i n g m a t e r i a l s are t h e s a p o g e n i n s , s u c h as h e c o g e n i n , b o t o g e n i n , a n d r i c o g e n i n . T h e s e s t e r o i d s a r e t o u n d in Mexican a n d Central American vines, a n d a r e c h a r a c t e r i z e d b y t h e p r e s e n c e of o x y ­ g e n in r i n g C . H e c o g e n i n p o s s e s s e s a k e t o g r o u p at t h e c a r b o n - 1 2 position, h u t a process has been w o r k e d out to m o v e this g r o u p t o t h e d e s i r e d 11 p o s i t i o n . I n a d d i ­ tion, a n alpha, beta u n s a t u r a t e d keto f u n c ­ t i o n h a s t o b e i n t r o d u c e d i n t o r i n g A in order to accomplish the cortisone synthe­ sis, b u t t h e p r o b l e m of c o n v e r t i n g a s a t u ­ r a t e d r i n g t o a n u n s a t u r a t e d o n e is f o r m i d ­

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a b l e . S a r e t t d e s c r i b e d a fruitful a p p r o a c h taken by Rosenkranz and others. V a r i o u s n a t u r a l l y a p p e a r i n g g r o u p s of steroids w e r e next investigated by Sarett, and they included ergosterol, cholesterol, stigmasterol, and various sapogenins. T h e s e materials d o not have the oxygen g r o u p in ring C , and t h e problem b e c o m e s o n e of i n t r o d u c i n g an o x y g e n g r o u p in t h e p r o p e r p o s i t i o n in t h i s r i n g . S a r e t t s h o w e d h o w v a r i o u s i n v e s t i g a t o r s , i n c l u d i n g F.vc i v t t W'allis, B e r g n i a i m , a n d H o s e t i k r u n / .

Synthesis

In d e s c r i b i n g s e v e r a l a p p r o a c h e s to t h e total s y n t h e s i s of c o r t i s o n e , S a r e t t f o u n d that t h e g r e a t e s t d i f f i c u l t y w a s e n c o u n t e r e d w i t h t h e n u m b e r of i s o m e r s w h i c h e x i s t as b l i n d a l l e y s o n the p a t h to t o t a l s y n ­ t h e s i s . T h e r e a r e 6 4 d i f f e r e n t o p t i c a l iso­ mers, a n d , inevitably, various s y n t h e s e s p r o d u c e d an i s o m e r w h i c h w a s l e a s t a b u n ­ d a n t b u t w a s of t h e n a t u r a l f o r m , w h i l e t h e m o s t a b u n d a n t — i n o n e case, six t i m e s as p l e n t i f u l — i s o m e r w a s of the u n n a t u r a l form. I n a d d i t i o n , t h e i n t r o d u c t i o n of c e n t e r s of a s y m m e t r y in t h e m o l e c u l e g a v e rise to m o r e i s o m e r s . N e v e r t h e l e s s , S a r e t t felt t h a t c e r t a i n a p p r o a c h e s had b e e n c a r ­ ried f a r e n o u g h a l o n g so that t r i c y c l i c p r o d u c t s o b t a i n e d c o u l d b e linked w i t h degradation products of naturally occur­ ring steroids. I n s u m m a r y , e n c o u r a g i n g progress has been m a d e in o v e r c o m i n g stereochemical p r o b l e m s a n d in laboriovislv b u i l d i n g s t r u c ­ t u r a l m o l e c u l e s w h i c h a r e on t h e p a t h t o cortisone. T h e b o t a n i c a l riddle h a s p r o b ­ a b l y b e e n s o l v e d , and an i n v e s t i g a t i o n of t h e c h e m i s t r y of p l a n t s a p o g e n i n s h a s b e e n begun. Medal

Presentation

O . L . H o v e r of t h e X o r t h J e r s e y S e c t i o n p r e s e n t e d t h e gold m e d a l , while G e o r g e Ba. j k e l a n d , B a k é l i t e C o . , p r e s e n t e d a c h e e k for S 1 0 0 0 .

Ε. Ε. Kimble, Pioneer in American G l a s s w a r e , Honored C&EN REPORTS: Scientific Apparatus Makers Association, Annual Meeting W H I T E S l ' L P H l Κ SPRINGS, \V. Y A . T h e c l i m a x of t h e t h i r t y - t h i r d annual m e e t i n g of t h e S c i e n t i f i c A p p a r a t u s M a k e r s A s s o c i a t i o n , h e l d h e r e A p r i l 15 to 1 8 , w a s t h e p r e s e n t a t i o n of t h e S A M A A w a r d for O u t s t a n d i n g Service to Evan E. Kinihle, p i o n e e r l e a d e r in t h e field of m a c h i n e a n d h a n d m a d e g l a s s w a r e a n d f o u n d e r of t h e K i m h l e G l a s s G o . , n o w a d i v i s i o n ot Owens-Illinois Glass C o . T h e SAMA award has heen presented only twice since t h e organization was founded. T h e two previous presentations were to Morris Leeds, founder a n d chair­ m a n ot t h e h o a r d , L e e d s & N o r t h r o p G o . , w h o w a s h o n o r e d in 1 9 4 9 , a n d t o H a r v e y X. O t t , a f o u n d e r a n d l o r m e r p r e s i d e n t ol t h e S p e n c e r L e n s G o . , n o w a d i v i s i o n of the A m e r i c a n Optical Go., w h o received t h e a w a r d in 1 9 5 0 . C o l . K i m h l e , w h o is S o , Hew f r o m h i s F l o r i d a h o m e to a c c e p t t h e a w a r d at t h e a n n u a l S A M A d i n n e r . P r e s e n t a t i o n of t h e e n g r a v e d , l e a t h e r - h o u n d a w a r d certificate

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w a s m a d e b y H . B. R i c h m o n d , c h a i r m a n of t h e h o a r d , G e n e r a l R a d i o C o r p . , a n d a p a s t p r e s i d e n t of S A M A . In his p r e s e n t a t i o n , Mr. Richmond c a l l e d C o l . K i m b l e " t h e person, m o r e t h a n any other individual, w h o made America I r e e o t E u r o p e a n i n f l u e n c e in t h e a v a i l ­ a b i l i t y of c h e m i c a l g l a s s w a r e , e s p e c i a l l y in a c c u r a t e t u n i n g . " C o l . K i m b l e l e d t h e fight at t h e e n d o f World War I " t o protect American-made c h e m i c a l w a r e t h r o u g h tariff p r o t e c t i o n s o that t h e U n i t e d States could s t a n d free a n d i n d e p e n d e n t f r o m its f o r m e r p o s i t i o n ot c o m p l e t e d e p e n d e n c e upon European sources," Richmond said. T h r e e scientific instrument a n d l a b o r a ­ tory a p p a r a t u s c o m p a n i e s were h o n o r e d at t h e S A M A d i n n e r w h e n t b e i r r e p r e ­ sentatives accepted membership certifi­ c a t e s for t h e i r c o m p a n i e s in t h e S A M A Century Club. T h e c l u b w a s f o u n d e d in 1943 to

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