May 20, 1958
149', [ a ] +127', ~" : : A 238 mp, log E 4.16; Anal. found for C18H2202: C, 79.65; H, 8.38) which upon microbiological dehydrogenationg with Corynebacterium simplexlo led in over 60% yield to equilin (VII), m.p. 237-240°, undepressed upon admixture with the natural hormone, [ a ] = +295', 282 mp, log E 3.36. The infrared spectra of synthetic and natural equilin were completely superimposable. Since the starting material, 19-nortestosterone acetate (I), is prepared5 from estrone which has been synthesized totally," the above reaction sequence also constitutes a formal total synthesis of equilin (V11). (9) T h e feasibility o f converting a 19-nor-A4-3-ketosteroid into the corresponding phenol with C. simplex already has been demonstrated with 19-norprogesterone (A. Bowers, C. Casas Campillo a n d C. Djerassi, Tetvahedron, 2, 165 (1958)), and with 19-nortestosterone (S.Kushinsky, J. Biol. Chem., 230, 31 (19.58)). (10) We are grateful t o Dr. Carlos Casas Campillo and staff for the microbiological incubation. (11) G. Anner and K. hliescher, Hela. Chim. Acta, 31, 2173 (1948); W. S. Johnson, D. K. Banerjee, W. P. Schneider and C. D. Gutsche, THISJ O U R N A L , 72, 1426 (1950); W. S. Johnson, D. K. Banerjee, W. P. Schneider, C. D. Gutsche, W. E. Shelberg a n d L. J. Chinn, ibid.. 7 4 , 2832 (1952).
RESEARCH LABORATORIES SYNTEX, S. A. .!.PARTADO
2597
COMMUNICATIONS TO THE EDITOR
POSTAL 2679
than one half of the label remained in the carbonyl group in each case. Simiarly, the reaction of 2naphthoyl chloride 0-18 with the silver salt of Nnitrocyclohexylamine yielded (via IV) nitrous oxide 0 R-0-C-R'
I1
ib
r
N=O
17-
11-N-C-R' II
' ILR-K A
CARLD JERASSI RECEIVED MARCH 29, 1958
INTRAMOLECULAR REACTIONS OF SECONDARY CARBINAMINE NITROSOAMIDES
Sir: Studies of the nitrosoamide reaction have shown' that the reaction proceeds in most cases with partial retention of configuration, and that there is an intramolecular path (b) for the formation of the ester. JVe now report2 an oxygen-1S tracer study
0
7
'
S-0-C-R
//
0
I
I1 I
R'C02H
+ S2 + Olefiri +1'
containing 0.0 atom % excess 0-18 and cyclohexyl naphthoate with 62'j?, of the 0-18 in the carbonyl group. Further information was obtained when
J. A. ZDERIC A . BOWERS HUMBERTO CARPIO
MEXICO, D. F.
+ Nf fl!
111
Iv
optically pure (-))N-(l-phenylethyl)-N-nitroso-2naphthamide-carbonyl-0-18 was rearranged. The partially racemized ester was cleaved, the 1phenylethanol obtained was treated with phenyl isocyanate, and the N-phenylcarbamate was fractionally crystallized. Samples of the DL form and the optically pure levorotatory form (corresponding to retention) were thus obtained. Analyses showed that both contained the same amount of 0-18 (Runs 3 and 4) ; the enantiomers are formed with the same distribution of 0-lS!
TABLE I Run
Cyclohexyl ( - ) 1-Phenylethyl 3 ( - ) 1-Phenylethyl 4 ( - ) 1-Phenylethyl % in c=O/o/o in ether 1 2
(I
Solvent and addend
CHaCOnH Dioxane 4CHZNZ* Dioxane 42HCOzH CH3C02H position.
Retn. of config.,
70
RKHCOR'
ROzCR'
Atom excess 0 - 1 8 R'CHzOH f ROH C/Ea
(-)ROH
(I)IZOII
58/42
0.536
0.537
69/31
U.381
0.380
0.798 .656
0.431
,545
65/35 55/45
.GO7
,696
,514
,592
,843
,372
74
1.233 1.232
0.611 ,622
80
1.232
81
1.232
Equilibrated methyl iiaplitlioate was obtairied.
of reaction b pertinent to the mechanism of the reaction and.to the problem of "intramolecular inv e r ~ i o n . " ~The nitroso derivatives of N-cyclowere hexyl and N-1-phenylethylnaphthamides-0-18 rearranged in various solvents; appropriate controls were run. The esters obtained were cleaved and the 0-18 analyses were run in the standard way.4 The results (Table I, C/E) show that although "mixing" of the label occurred in reaction b, more (1) (a) E. H. White, THISJOURNAL, 7 7 , 6014 (1955); (b) R . Huisgen, Ann., 601, 21 (195fi); also earlier articles. (2) Our 0-18 results for primary carbinamines were reported in Abstc. o f the 130th A.C.S Rleetina, September 18, 3956, p. 20-0. (3) C . I?. Rouzer nncl IC. S. r.ewis. 'rlrrs J u u K N n l . , 76, :iI82 ( ~ w x { ) , (4) W. IC Ihwrinx ; t n r l I t . l h d n i : k n , ;hid., 7 6 , $:!I5 (l!j5:;),
A mechanism involving partial mixing of the oxygen atoms prior to the step in which the final configurations are determined accounts satisfactorily for the results; the loss of nitrogen from V or VI could reasonably lead to bond formation on both
I1
0 I1
k
+ I11
+ RS2@00-C-R' V
k'it RNz@00'8-C-R' I!
rj
VI
k
> k'
7
sides of the plane of II. \vklITh HOPKINSCNIVERSITY BALTIMORE18, MARYLASD STERLIXG CHEMISTRY LABORATORY YALE UNIVERSITY CARLA. AUFDERMSRSH, JR. X ~ l vHAVES, C ~ N ~ E C T ~ C ~ T RECEIVED MARCH6, 1958 REMSEs
HALL
THETOHSS
BOOK REVIEWS The Carbohydrates. Chemistry, Biochemistry, Physiology. Edited by \YARD PIGMAN,Department of Biochemistry, University of Alabama Medical Center, Birmingham, Alabama. Academic Press, Inc., 111 Fifth Avenue, 902 pp. 16 X 23.5 cm. Yew York 3, N. Y. 195i. xvii Price, $80.00. T h e present text and reference book represents an exceptionally extensive revision and expansion of “Chemistry of the Carbohydrates,” first published in 1948 by Professor Pigman and Dr. R . h1. Goepp, Jr. T h e earlier edition, which was the first extensive general treatise on carbohydrate chemistry in the English language, and which was received enthusiastically by carbohydrate chemists and biochemists, has been brought up t o date through 1956 in the current first revision. In contrast to its predecessor, the present text is written b>-Professor Pigman, also its editor, with the aid of some twenti- contributing authors, all active research specialists in some branch of carbohydrate science. In view of the tremendous and rapidly growing literature in this field, this departure gives the present volume greater breadth of scholarship than would be conceivably possible under single authorship. T o the editor’s credit the divided authorship is completel>-unobtrusive, atid the reader receives a pleasant impression o f uniformity and homogeneit>- on continuing from chapter to chapter through the book, a feeling augmeuted, perhaps, bl- the editor’s adoption of tlie neiv official rules of nomenclature wherever applicable throughout. The chapter headings in the present volume indicate a geuerally similar organization t o t h a t employed in the earlier edition. The first ten chapters, treating mainly the chemistry of the simple sugars and their derivatives, are revised mainly b y expansion to include more recent material. This expansion averages an approximately 237;. iiicrease iu the number of pages in each of these chapters. The later chapters of the earlier edition, dealing with polysaccharides, have been more extensively changed, and the detailed treatment of starch and cellulose has been abbreviated in favor o f more general information regarding plant, bacterial, fungal and animal polysaccharides. 111 addition, ne\v chapters covering the Identification and Quantitative Determinatioii o f Carbohydrates, Photosyllthesis and Metabolisin ,if Carbohh-drates,ant1 Carbohydrates iii Sutritioii have beeti iticlutlcd. Those subjects which 110~1. more cursory ci)nsideration are :tdequatcly covered ’r inonographs, to which referencc is always g i w i i l l tlic present trcati>c. 111 general, frequent references to iiinre detailed treatments help to increase the coverage of the test. The expantled informatiou and scope of the present volume over its predecessor is reflected in an increase in the nuiiiber of t11v t c s t x i l pages from t i 4 i to 817, the pages ( I f ciiitlior itides f i n l i n 20 t t l :%Ia i i i l the iiuiiiI)cr of f ( ~ t ) t i i r ) t c fsr o i i i
+
For a text of its size the present volume appears reniarkably free from tjpographical errors. In view of the considerable selection of material froin tlic literature which such a treatise requires, the reader mal- perhaps disagree occasionally and trivially n-ith the various authors on their emphasis. Similarly, such points as this reviewer found a t all objectionable on first reading proved rather unimportant 011 re-examination in the light of the over-all mvriuniental task of the revision. Designed as both a textbook and a referencc book, tliis volume fulfills both functions aclmirablh-. Thc geiierul excellence arid coverage will ensure its purcliase bh- every practiciug organic chemist, biochemist and medical rcscarcli worker concerned with the c1ieniistr)- of carbohydrates for :I long time to come. DEPARTMEST OF CHEMISTRS
STANFORD USIVERSITY STANFORD UNIVERSITY, CALIF.
\VILLIAM A. BCJSNER
Advances in Catalysis and Related Subjects. Volume IX. Edited by D. L). ELET, Sottingham, England; FRASKESBURG, Lancaster, Pennsylvania; and KOMARETVSKY, Chicago, I h O Proceedings of tlie 3, Philadelphia, PennInternational Congress 011 Cata sylvania, 1956. Edited by AD E R T FARKAS, Houdry Process Corporation, Marcus Hook, Pennsylvania. Academic Press, Inc., Pul>lisliers, 111 Fifth AvenueL S e w Tork 3 , S.Y., 1957. xviii 84i pp. 16 X 23.0 cin. Price, $16.00. The ninth volunie of “.kivaiices in Catalysis” series consists essentially of the papers presented a t the Internatioiial Congress on Catall-sis a t Philadelphia in 1956. It is thus different in format and content from the preceding eight volumes ivliich consist of reviews and interpretations o f selected scctiocs of tlic massive literature of catalysis. There is 110 doubt t h a t t h e material of \-olunie I>; belongs in this distinguished series, because thc sum total of these papers represe,its a thorough and modern review of catalysis as the subject was conceived in 1956. This is indeed a wortlij- climax to the efforts of the late \Y.G. Frankenburg arid 1.. I. Komareivsky toward bringing together from world wide source? the best thought oii catal!-tic clleniistry. I )r. H e y and I l r . Iiarkas arc to lie comnirntlec! for ci~iii~)letiiig this task \\-it11 1111 cicln>- d t e r thc d e a t h o f tlieir editorial collaborators. Mati,- outstxiitliug scientists spccializing iii catalysis ha\ e coiitributed to this rolunie. T h e orgaiiizers of the International Congress on Catalb-sis are to be coiigratulated nrrt ~IIIIJfor :is.;eiiil)liiig this wiirthwhile program but for ci,nsolit1:itiitg tlic :~~liici-ct~iciits of t h e Ciitigrcss b! securitig ~ ) t t I ~ l i c a to if ~tlic ~ i ~i)aj)crs i i i tliis urcful fi~rtii. f v i - t ~ i i v ct ~I a1)iiut GIII)i r i t l i t itlual ‘1‘11~’(1 Ii:tpei.s 3114tlic iiiii-i~iIucti~~i~* iiy l i ~ y l iS . ‘ J ’ i t ~1131I i i i ~ I c ~i \\ S ~ I I I ~ V W ~ I : ~ ~ tli~kiiletl, :iii,l k ‘ i i c . L . l < i ( i c , i l w i w i ~ ~ i t ~ t r i l i a t c11) ~ c l1 4 7 x , i v t i t i < t \ ~ I O ~ I I i i c Y ~ 1 e : l s f~~~- , l l l l‘SI, 1 4 , ;I2 ILIgl’.. (1
+
