COMMUNICATIONS TO THE EDITOR
1248
1-01. 6.3
above products accounted for over 85% of the total crystalline sterols. The mother liquors from pennogenin, however, Sir: contain relatively smaller amounts of two new We have investigated the steroidal sapogenin sapogenins, m. p. 263 and 180', which we have fractions from Beth root collected a t seven different named nologenin and fesogenin, respectively. localities during the past two years. One of these Both give precipitates with alcoholic digitonill lots was obtained from S. B. Penick and Company. arid give tests for unsaturation. We have found that diosgenin accounts for 33Sologenin, having the composition CZHUOS, OUa/, of the total steroidal sapogenin fractions. W;LS isolated from the crude crystalline pennogeniii From the mother liquors of the crystalline dios- fraction. Anal. Calcd. for C27HA4O;: C, 72.3; genin acetate was obtained kryptogenin acetate H, 9.b. Found: C, 72.3; H, 9.3. Boiling acetic [Marker and co-workers, THISJOURNAL, 65, 739 anhydride formed a &acetate, m. p. 180". Anal. (1943)], m. p. l N " , in 20-40% yields. Hydroly- Calcd. for CalH4807: C, iO.0; H, 9.1. Found: C, sis of the mother liquors from kryptogenin acetate iO.0; H, 9.2. Although its solubility and meltgave a new steroidal sapogenin having the com- ing point correspond to those of chlorogenin, the position C27H42O4, m. p. 247', which we have two compounds are readily differentiated by named Pennogenin. Anal. Calcd. for C2iH4204: their analyses and the melting points of their aceC, 75.3; HI 9.8. Found: C, i4.9; H, 10.0. tates. The yields of the latter varied from 10-20oJ, of Fesogenin having the composition C27H4003 was the total sapogenin fractions. Two of the oxy- isolated from the mother liquor of the crude crysgen atoms are present as hydroxyl groups, one of talline pennogenin fraction. Anal. Calcd. for which acts with boiling acetic anhydride to form C2,H4,,03: C, 78.6; H, 9.8. Found: C, 78.3; a monoacetate, m. p. 200". Artal. Calcd. for H, 9.8. Catalytic hydrogenation using pallaC2YH4406:C, 73.7; H, 9.4. Found: C, 73.6; dium-barium sulfate catalyst gave dihydrofesoH, 9.6. Pennogenin shows no ultraviolet absorp- genin, m. p. 213". Anal. Calcd. for C27H~203: tion for a free carbonyl group. Prolonged treat- C, 75.2; H, 10.2. Found: C,77.8; H, 10.2. ment of pennogenin (I) with ethanolic hydro- Reduction with sodium in alcohol gave tetrahychloric acid gives kryptogenin (11). We propose dro-fesogenin, m. € 2 . 2-10", Anal. Calcd. for structure I for pennogenin. Cz7H4403: C, Ti.8; H I 10.7. Found: C, 77.6; H, 10.6. These reduction experiments indicate a conjugated system. The details of the isolation work and structure proof will be given in a forthcoming issue of THISJOUKNAL. We thank Parke, Davis arid Company for their help. STEROLS. CLV. SAPOGENINS. LXVII. PENNOGENIN, NOLOGENIN AND FESOGENIN, THREE NEW SAPOGENINS FROM B E T H ROOT
c o I I1 c-c-c-c-c
A$P
SCHOOL OF CHEMISTRY AND PHYSICSRUSSELL E. MARKER THEPENNSYLVANIA STATE COLLEGE R. B. WAGNER STATE COLLEGE, PENNSYLVANIA DALEP. J. GOLDSMITH PAULR. ULSHAFER CLARENCE H. RUOF RECEIVED AYRIL20, 1943
/!-OH \C
C H b - j
A'
I
/ / / HO./lLW 11. Kryptogenin
In each of the sapogenin fractions isolated from the seven different sources of Beth root, the three
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STEROLS. CLVI. SAPOGENINS. LXVIII. THE STEROIDAL SAPOGENIN FROM B A L A iVI?'ES A EG I'P TICA (WALL.)
Sir: Kon and Weller [J. Chem. SOC.,800 (1939)l have reported the isolation of a new steroidal sapogenin, nitogenin, from the kernels of Balanites aegyptica (Wall.). Its properties have been described as follows: m. p. 201 ', [aID - 112' in chloroform, Anal. C, 77.6; H, 10.5; acetate,
June, 1943
COMMUNICATIONS TO THE EDITOR
1249
m. p. 1 9 2 O , Anal. C, 76.1; H, 10.0; benzoate, thors.a The values of h and g established by m. p. 229 ", Anal. C, 78.2; H, 9.1. This material Stonehill and Berry are, however, not final. The differed from tigogenin and sarsasapogenin by fundamental constants given by Birge4 differ direct comparison. However, the authors failed somewhat from, and supersede, those listed by to note its similarity to diosgenin. Thus, dios- Childs and used by Stonehill and Berry in their genin isolated from Dioscorea tokora [Fujii and calculations. On the basis of the Birge constants Matsukawa, J . Phurrn. SOC.Japan, 56,408 (1936)l e = 4.8025 X 10-lo e. s. u. (instead of Childs' has the following properties: m. p. ZOO", [ a ] l g D 4.803 X lO-'O), k = 1.38047 X erg/"C. - 119' in chloroform, Anal. Calcd. for C27HaO3: (instead of 1.379 X 10-l6), N = 6.0228 X loz3 C, 78.2, H, 10.2.; acetate, m. p. 190", Anal. (instead of 6.028 X loz3),TO= 273.16 (instead of Calcd. for C29H4404: C, 76.3; H, 9.7.; benzoate, 273.15) and on the basis of Wyman's6 value 78.54 m. p. 237", Anal. Calcd. for C34H4601: C, 78.7; for the dielectric constant of water a t 25" we find H, 9.0. h = 0.5091 and g = 0.3286 X los. Calling d and We have obtained a sample of palm kernels iden- t the ratios D/78.54 and T/298.16 we have, in tified for us as Balanites aegyptica. The sapo- general genin fraction contained diosgenin as its principal I t = - 0'5091 and = 0.3286 X 108 (dt) (dt)'/2 constituent. The identification was made by the melting point and mixed melting point determina- The revised constant 1 for the osmotic coefficient tions on the free genin, 206"; acetate, ZOO"; and formula benzoate, 238". Catalytic reduction of its ace1 - G = ZZizzd.o(gad7) tate gave tigogenin acetate, m. p. and mixed m. p., 202". A mixture containing the latter and the is 0.3908 for water a t 25" and, in general original acetate melted 186". 1 = 0.3908/(dt)3/1 We thank Parke, Davis and Company for their (3) On the basis of the constants tabulated by Fowler in hi:; 'Statistical Mechanics" (Cambridge University Press, 1936) Van help. Rysselberghe and Eisenberg (THISJOURNAL, 61, 3030 (1939), 61, 431 RUSSELLE. MARKER (1940)) and Eisenberg (Thesis, Stanford University, 1942) used the R. B. WAGNER values h = 0.5059 and g =0.3287 X 103. SCHOOL OF CHEMISTRY AND PHYSICS DALEP. J. GOLDSMITH (4) Birge, Reo. Mod. Phys., 13, 233 (1941). THEPENNSYLVANIA STATE COLLEGEPAULR. ULSHAFER ( 5 ) Wymun, Phys. Reg., 36, 623 (1930). H. RUOP DEPARTMENT STATECOLLEGE,PENNA. CLARENCE OF CHEMISTRY RECEIVED APRIL21, 1943 OF OREGON UNIVERSITY EUGENE, OREGON PIERRE VANKYSSELBERCHE RECEIVED FEBRUARY 19, 1943 FURTHER REVISION OF THE CONSTANTS OF THE DEBYE-€#CKEL THEORY
CONSTANTS OF THE DEBYE-HUCKEL THEORY
Sir :
Sir :
In a recent note Stonehill and Berry' have published revised values for the constants h and g in the Debye-Huckel expression for the logarithm of the activity coefficient of a zl,zz-valent electrolyte in aqueous solution a t 25"
In accordance with the revised constants of Birge quoted in the preceding Communication of Dr. Van Rysselberghe, the equations of Scatchard and Epstein' for the Debye-Hiickel limiting-law expressions in terms of concentrations in moles per kilogram of water should also be revised to give
+ 0.15471 (t/100) + 0.03569 (t/ioo)* + 0.02389 (t/100)31 = 3.470 x lo-* [I + 0.10194 (t/100) + 0.04269 (t/100)* + 0.00976 (t/100)8] = 0.3240 X lo8 [l + 0.05217 (t/100) - 0.00916 (t/100)* + 0.00888 (tllOO)~]
In Yk/Zk'
On the basis of the physical constants tabulated by Childs2they find h = 0.5103 and g = 0.3290 X lo8. They indicate some of the possible implications of this change from the values h = 0.5063 (or 0.3056) and g = 0.3287 X los (or 0.3288 X LOx) based on the old values of the fundamental constants and used so widely by numerous au(1) Stonehill and Berry, T H I 5 JOURKAL, 64, 2724 (1042). (2) Childs, "Physical Constants," Methuen, London, 1U3Y.
di
= 1.1244 [1
In YL/Zk2K K/v'G
in which Y k is the ratio of the activity of the k'th ion species to its molality, zk is its valence, t the centigrade temperature, ,u the ionic strength, (1) G. Scatchard and L. F. Epstein, Chem. Rev., SO, 211 (1942).
