mole) ; n-butyric acid, 35.9% (0.0034 mole) ; n-butyl n-butyrate, 27.3% (0.0010 mole) ; nbutanol, 3.770 ; n-butyraldehyde, 0.8% ; propionic acid, 0.9Yc; n-butyl propionate and n-propyl nbutyrate, traces; and an unknown hydroxy (?) acid, 1.37,. The analysis of the major component was confirmed by conventional chemical separation and identification. We wish t o thank the California Research Corporation for support which made this investigation possible.
On this basis, we suggest this fortiiula for the structure of formazans obtained from polysaccharides, e.g., from starch, oxidized with periodic acid CH,,
CH,OH
N
DEPT OF CHEMISTRY ATD CHEMICAL EVGI~EERISG STANFORD UUIVERSITI. HARRYS X ~ O S H E R STATFORD, CALIF CHARLES F ~VURSTER RECEIVED SEPTEMBER 6, 1955
N
0 b h’
N
N
0 b \”
Procedure.-The polysaccharide samples were oxidized at room temperature with 3 t o 5y0sodium metaperiodate for 24 and 48, and in the case of inTHE FORMAZAN REACTION IN PROVING THE soluble polysaccharides (e.g., cellulose or xylan) for STRUCTURE OF PERIODATE OXIDIZED POLYSACCHARIDES 120 hours, respectively. The corresponding phenSir: ylhydrazones were prepared as described by Barry Iiie have reported’ that the aldehydo-phenyl- and Mitchell. The bright yellow phenylhydrahydrazones of sugars couple with diazo compounds zones were then dissolved or suspended in pyrito build formazans, but that the phenylhydrazones dine or a 1 : 1 mixture of pyridine and ethanol. of ring structures derived from the hemiacetal Dropwise addition with ice-cooling, of a diazotized form do not. U’e now propose t o make use of aniline solution led to coupling to give the formathis observation in a study of the precise structures zan. The vividly red solution or suspension was of polysaccharides oxidized with periodic acid and poured into ice water, and the polysaccharide formazans separated. With concentrated sulfuric of the phenylhydrazones obtainable from them. 2 , a with polysaccharides oxidized with periodic acid they yielded the dark-blue color-reaction acid, each indi~idualoxidized monosaccharide re- characteristic of the formazans. By regulating the rate of oxidation it is possible acts with only one mole of aromatic amine, e.g., of phenylhydrazine.4 In the literature the following to determine how many formazan groups form per three formulas are suggested for the tnonosac- monosaccharide group. For instance, if a cellulose wad is oxidized for 120 hours as described by chari~les,~ and , ~ their p h e n y l h y d r a z ~ n e s ,respec~~~ Tawne and Satre,3 it will contain only one formatively. _ _ + zan group t o three monosaccharides, and retain its original fibrous structure. Anal. Calcd. for the phenylhydrazone (C24H34014N2)z: N, 4.88. Found: N, 5.04. 0c cH Calcd. for the formazan (C30H&4N4)p: ,,,\ o OH N - N H - 0 HO N OH N, 5.26. Found: N, 7.42. If potato starch is oxidized with 3‘); I 11 111 sodium metaperiodate for 24 hours, or inulin with 470 sodium metageriodate (1) is an aldehyde-heniiacetalpheriylhydrazone, for 48 hours, the resuiting product will ~ 0 1 1 I I, a hemiacetal-aldehydo-phenylhydrazone,aiid tain two forniazan groups to three monosacchnI 11, a “hemialdal” structure. Of these, only I1 rides. contains an aldehydo-phenylhydrazone structure A n d . Calcd. for the phenylhydrazone (C30Haasuitable for yielding a formazan. N 4 0 1 ~ ) ~N, : 8.46. Found: N for starch, 8.31; On coupling with diazotized aniline in ice-cold for inulin 8.40. Calcd. for the formazan (C42H46pyridine solution, the phenylhydrazones of several NsOIJs: N, 12.87. Found: N for starch, 11.80; polysaccharides (cellulose, starch, inulin, xylan and for inulin, 12.50. dextrin) oxidized wirh periodic acid, we obtained A xylan sample oxidized with 3 7 , periodate solubright-red diphenyl-formazans, and thereby ob- tion for 120 hours and a dextrin sample oxidized tained unambiguous proof of the presence of struc- for 48 hours applying the above-described proreture I1 in these compounds. [lure likewise yielded the corresponding poly(1) I,. Mester and A. Major, T H I S J O U R N A L , 77, 42W (19%). saccharide formazans. (Found: N for xylatl 1 2 ) E. I,. Jackson and C. S. Hudson, ibid., 59, 2049 (1937). 11.10; N for dextrin, 12.03). (3) G. Jayme and >I, Satre, Rei.., 77, 242. 248 11044). This new reaction, yielding sparingly soluble ( 4 ) V. C. Barry and P. W. D . Mitchell, .I. Chein. Soc , %020(1954) ( 5 ) V. C . Barry, J. E. McCormick and P. W. D. hIitchell, ibid , 3642 formazans of vivid red color and high nitrogen con11454). tent, will facilitate establishing as yet undecided (6) J . H. Mitchell and C. B. Purves, THIS J O U R N A L , 64, 589 (1942). structures of polysaccharides. ( 7 ) J. VJ, Rowell, P.H. Forziati and R . E . Reeves, ibid., 73, 4484 (1951). Experiments to form new active groups (tetrazo(8) Z. A . Rogovin, A , G. Jasunskaia and Ti. M. Hogoslovskii, liums, thioaldonic-acid-phcnylhyrazides,metallic .I PviklotI;i~17( ‘ / i , m i j , i , 23, G R I fl950). ( Y ) \. c I i u r r v I ) \\’ I \ l i t < , l ~ ~ l 1. l , Tlrrni .S)’ , T1.831 ~ 1 ~ I - i ~( ~ ~ n ~ p l e u iens )tlir riiolrculc o f polys~iccliarides bv
0-HN-NH
.LII,~
I
ei)-O
“-0
Oct. 20, 1955
BOOKREVIEWS
way of transformation of formazan groups,l0I
are
in progress. Thanks are due to Prof. G. ZernplCn for valuable (10) V. C. Barry, Nafurc, 162, 537 (1943). (11) V. C. Barry, T. Dillon and W. MeGottrick, J . Chem. SOL., 183 (1942).
3-43
advice given and to E. Moczar for assisting in the experiments.
eHEMIsTRY I~~~~~~~~ oRGAXrC TECHNICAL UNIVERSITY
L. MESTER
BUDAPEST, HUNGARY
RECEIVED JUXE 16, 1955
BOOK REVIEWS Synthetic Methods of Organic Chemistry. An Annual Sur- The chemist interested in fundamental studies will find vey. Volume 9. By W. THEILHEIMER.Interscience quoted many of the postulated mechanisms of chemical Publishers, Inc., 250 Fifth Avenue, New York, S. Y. reaction such as oxidation, hydrolysis, pyrolysis. Though 491 pp. 16.5 X 23.5 cm. Price 118.90. 1955. xvi it is unthinkable that he would agree with all of the mechaNine years ago this reviewer had the privilege of com- nisms presented, they represent the latest published hypothementing on the first volume of Theilheimer’s “Synthetic ses. The presentation is factual; the editing, excellent. Methods.” Xow the ninth volume has appeared, covering the years 1952-1954: the author is to be complimented upon Errors are a t a minimum. For the kineticist it is recomhaving kept abreast of the ever-swelling tide of research re- mended reading; for the applied polymer chemist it should sults and upon having done so with adherence to the high be a required course. principles formulated a t the outset. PLASTICS DIVISIONRESEARCH DEPT. An added feature, presented beginning with Volume VIII, OF AMERICA 0. V.LUKE,J R . CELANESE CORPORATION consists in a few introductory pages of “Trends in Organic SGMMIT, SEW JERSEY Chemistry” in which the author presents a condensed survey of synthetic methods recently introduced, perfected, modified, or disinterred, that appear to be of broad significance and Related Phenomena. Physical Chemisand applicability; there is, e.g., a paragraph devoted to Solubilization try. A Series of Monographs. Volume IV. By MARY methods of peptide syntheses. DeEVELYNLAINC MCBAIN A N D ERIC HUTCHINSON, The series has, to all intents and purposes, become one of partment of Chemistry, Stanford University, Stanford, the standard resources of every research library, and this California. Academic Press, Inc., Publishers, 125 East reviewer feels that any further discussion of the collection, 23rd Street, Sew York 10, S. Y. 1955. xv 259 pp. including the good-natured controversy over the system of 15 5 X 23.5 cm. Price, $7.00. symbols, would be redundant if it were to go beyond an exAlthough dedicated to the memory of J . W.McBain and pression of gratification a t the successful continuation of a introduced by a selection from his writing, this book is not very worthwhile enterprise. a compilation of contributions from the Colloid Chemistry RESEARCH DEPARTMENT a t Stanford University, but a n attempt to organize PRODUCTS, Ixc. CIBAPHARMACEUTICAL HANSHEYMANX Group the voluminous literature on solubilization and to proceed SUMMIT, NEW JERSEY as far as the state of knowledge permits toward a theoretical treatment of the subject. The fact that the concepts the authors advance in the light of recent work on colloidal elecPhysical Chemistry. A Series of Monographs. Edited by trolytes are sometimes at variance with those supported by ERIC HUTCHINSON,Stanford University, California. Professor McBain during his active research in the field does Srolume 111. Degradation of Vinyl Polymers. By not disturb them and would probably not have troubled H. H. G. JELLINEK,Senior Lecturer in Physical and In- McBain, who had a thorough respect for the logic of experiorganic Chemistry, University of Adelaide, South Aus- ment. tralia. Academic Press Inc., Publishers, 125 East 23rd The phenomena of solubilization by strictly micellar sysStreet, Xew York 10, N. Y . 1955. 329 pp. 15.5 X 23 tems are presented in a brief but excellent historical chapter cm. Price, $8.50. and in a longer chapter bearing the noncommittal title, The author states, and the reader will concur, that the “Data and Facts of Solubilization.” The latter, which book should be of interest to the polymer chemist concerned occupies nearly half the book, is in fact a well organized with fundamental aspects of degradation reactions and also and readable survey into which the authors have introduced a to the polymer chemist in the applied field. The latter may considerable body of stimulating discussion based on their be somewhat dismayed by the montage of differential equa- view of solubilization as a partition between the solvent tions confronting him in the first chapter. If he will begin proper and a micellar pseudo-phase. The chapter opens a t page 31, he can avoid much of the mathematical deriva- with a summary of the experimental methods available for tions and will find the ideas and experimental data just as the study of solubilization. This is brief, in keeping with interesting. the condensation characterizing most of the volume; it is The author demonstrates an excellent familiarity with the regrettable that the scale of the work does not permit a more whole field of polymer degradation. The book is admittedly detailed and critical consideration of the experimental prowritten from the standpoint of reaction kinetics and is a cedures and the assumptions implicit in their use. The theoretical treatise of mechanisms of polymer degradation. remainder of the chapter is devoted to the effect of such However, considerable experimental data are presented, variables as constitution, extraneous solutes, temperature much of it the work of the author himself. Chapfers 2, 3 and mixed micelle formation, with specific sections on emuland 4 will be o f especial interest to the applied chemist in the sion polymerization, solubilization in non-aqueous systems field of polymers. Since this chemist is interested in the and solubilization phenomena in two-phase systems. In degradation of polymers from the standpoint of being able to the effort to compress a large volume of information into prevent that degradation, he will find fruitful suggestions small compass it is perhaps inevitable that minor inaccuraand ideas coming into his mind while digesting the author’s cies should appear: those noted do not affect the major consuggested mechanisms. He will, however, be disappointed clusions drawn and will not be listed here. that the very important field of photodegradation of polyThere is a relatively detailed preliminary chapter on the mers is relegated to one paragraph each in the chapters on formal thermodynamics of micellar systems arid on the “ T ) e y r d ~ t i t mit] Soltitioil sild Bulk Degradntiuri i n P I U C ~ I D . ” tnethotls for measuring the critical micelle comcemtratiou.
+
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