X-Ray Diffraction Powder Data for Steroids JONATHAN PARSONS and WILLIAM T. BEHER The Edsel B. Ford Institute for M e d i c a l Research, Henry Ford Hospital, Detroit 2, M i c h .
X-ray diffraction powder data and powder diffraction photographs for 27 steroids are presented. Visual comparison of the powder patterns for known and unknown steroids was found to be sufficient for identification.
Table 11. Powder Diffraction Data for Steroids d , A.
1. Estriol 8.08 3 6.73 8 6.05 5 4.81 3 4.34 10 4.16 4 3.36 3 2.85 2 2.47 2 2.28 2 2.11 1 1.88 3
L
ARGE numbers of well crystallized organic compounds exist
which give x-ray diffraction patterns satisfactory as a means of identification when their pattern data are available. Most of the steroid group of compounds fall into this category. Bernal, Crowfoot, and Fankuchen ( 1 ) published crystallographic and optical data for some 80 sterol derivatives but did not include powder diffraction data. The purpose of this paper is to present powder data for 27 steroids. PROCEDURE
The melting point of each compound (Table I ) mas determined and checked with the literature to be certain of the purity and identity of these steroids. The crystals were powdered in a
Table I.
Index to Steroid X-Ray Diffraction Powder Data
Pattern Name
KO.
Melting Point (Uncorr.), ' C.
d , A.
CIS STEROIDS 1 2 3
280-282a 259-261 176-179
A1 A2 A3 A4
C19-29 STEROID^ A. Monohydric Alcohols Stigrnasta-A5.22-dien-3(p)-ol (stigmasterol) A5-Cholesten-3(@)-01(cholesterol) Cholestan-3 (p)-ol (dihydrocholesterol) Ab-Stigmasten-3 (@)-ol (13sitosterol)
167-169 146-148 141-142 138-140
B1 B2
B. Dihydric Alcohols A5-4ndrostene-3(8), 17(@)-diol A5-4ndrostene-3(8) ,17(p)-diol-17-benzoate
180-182 218-220
c1 C2
C. Diketones A4-.4ndrostene-3,17-dione A4-Pregnene-3,20-dione (progesterone)
172-174 120-122
D2 D3 D4 D5 D6 D7 D8 D9 D10 D11
El E2
D. Monohydroxy-Monoketones AS-Androstene-3 (@)-o1-17-one(dehydroepiandrosterone) AS-Pregnene-3 (p)-ol-20-one (pregnenolone) Ar-Androstene-l7( a)-ol-3-one (testosterone) As-Androstene-3(@)-01-17-0ne-3-acetate (dehydroepiandrosterone acetate) Androstan-3(u)-ol-17-one (androsterone) AS,lO-Pregnadiene-3 (p)-ol-20-one (dehydropregnenolone) 16,l 7-Epoxy-AS-pregnene-3(p)-ol-20-one-3acetate (epoxypregnenolone acetate) AS-Pregnene-3(P)-ol-20-one-3-acetate (pregnenolone acetate) 17(p)-methyl-A4-androstene-17 (a)-ol-3-one (methyltestosterone) As-Pregnene-3(,9)-01-2O-one-3-methyl ether (pregnenolone methyl ether) As--Pregnene-B(p) ,21-diol-20-one-21-aoetate (acetoxypregnenolone)
E. Monohydroxy-Monocarboxyacids 3 (@)-Hydroxy-bisnor-AS-cholenicacid 3(p)-Acetoxy-bisnor-A~-cholenic acid
Ill1
d , A.
-R
_1_9
2.94 2.66 2.42 2.27 2.22 2.14
151-153 191-193 152-155 168-170 184-185 173-175
I/Il
3. Estradiol 7.50 4 6.71 9 6.03 4 5.64 10 5.00 4 4.78 9 4.63 4 4.32 6 4.08 4 3.92 6 3.72 5 3.35 6 3.24 3 3.13 3 3.02 3 2.90 2 2.80 4 2,65 1 2.56 2 2.49 4 2.40 2 2.32 1 2.27 2 2.21 2 2.14 4 2.08 2 2.00 2 1.93 3 1.86 2 1.79 2
I/Ii
STEROIDS A. Monohydric Alcohola A I . Btigmasta-42. AS-Choles8 3 . CholestanA5,22-dien-3(@)-01 ten-3(,9)-01 3(8)-01 12.9 6 17.0 3 17.0 4 9.21 4 13.4 13.6 3 7.87 11.4 11.3 7 3 6.69 9.26 8 9.76 6.30 8.43 2 7 8.76 6.01 7.76 7.31 8 2 5.77 6.86 6.71 6 6 5.50 6.26 6.21 1 6 5,13 5.74 5,59 10 9 4.75 5.26 10 5.17 5 4.47 4.76 6 4.91 ? 4.25 4.52 4.58 4 ? 4.05 4.33 4.22 3 3.88 3.97 5 1 4.10 4 3.45 3.80 4 3.58 3 3.41 2
d , A.
I/Ii
29
-44. As-Stigmasten-3 (8)-01
2
1 1 1
2
1
3
B. Dihydric Alcohols B2. As-Androstene-3(8),17(@)AS-Androstene-3 (p),17(a)diol diol-I7 benzoate 10.8 6 3.11 5 14.9 2 2 92 2 7 8.47 3.02 3 2 5 8.31 2 83 2 7.09 i 2.94 7.38 2 78 7 6.05 2.82 10 5 6.05 2 72 2.71 4 5,87 10 6 5.59 2 59 5.58 2.58 10 5.32 10 5 1 5.39 7 4 2.56 5.02 5.00 4.67 4 8 7 2 32 2.48 4.82 4 2.38 5 4.50 2 22 4.50 6 2.31 4.30 7 2 13 4.28 2.10 3.92 2 09 6 6 4.09 3.69 5 6 2.05 2 03 3.85 6 5 1.98 3.59 1 96 1 3.72 1 6 1.94 3.47 2 3.60 3.35 2 1 1.87 3.46 2 2 1 1.78 3.23 7 3.38 1 2 1.73 3.14 3.27 5 2 3.05
B1.
155-158 149-151
2
161-164 125-127
5 1;
183-185
291-293b 234-236
BILE ACIDS F1 Cholic acid F2 Desoxycholic acid F3 Dehydrocholic acid a 4' rise per minute. b Decomposed.
d , -4.
C19-
Estriol Estrone Estradiol
D1
I/Il
d , A.
d , A. I/Il CIBSTEROIDS 2. Estronea 9.36 2 7.26 2 5.56 2 6.19 6 5.85 9 5.13 7 4.85 8 4.40 10 4.01 6 3.85 6 3.70 5 3.59 1 3.27 6 3.18 1 3.14 5 3.01 1 2.94 5 2.74 2.57 6 2.44 4 2.43 4 2.36 4 2.23 6 2.17 2 2.10 2 2.06 2 2.01 6 1.95 2 1.92 2 1.88 1 1.79 1 1.74 1 1.70 1 1.65 1
1/11
196-1 98 171-173 23 4-2 36
a
514
Six-sided plates.
(Continued m page 516)
515
V O L U M E 27, NO. 4, A P R I L 1 9 5 5
Figure 1. X-ray diffraction powder patterns of steroids Key found in Table I
ANALYTICAL CHEMISTRY
516
Table 11. Powder Diffraction Data for Steroids (Continued) d , A. 1/11 d, A. (Continued) C. Diketones C2. A4-Pregnene-3.20-dione C1. A4-Androatene-3,17-dione 10.4 1 2.98 5 3 2.80 8.51 1 6 8 2.69 7.09 7 1 9 6.71 2.51 1 6 7 2.43 6.01 10 5 7 5.57 2.38 7 3 10 5.16 2.31 4 9 7 4.68 2 2.24 4 4 4.45 2.12 3 5 4 4.24 2.08 2 8 5 4.00 3 2.03 4 7 3.66 4 2.00 4 3 3.53 1.95 7 3 6 3.19 6 7 3.13 2 1 3.05 2 1 d , A.
1/11
1/11
d , A.
C10-29
d , A.
1/11
1/11
6TEROID0
d , A.
d , A.
1/11
(8) 2 3 2 3 3 2 2 3 3 2 2
2
3 2 2 3
1/11
D. Monohydroxy-Monoketones D1. AS-Androstene3(p)-ol-17-one D2. A6-Pregnene-3(@)D3. ALAndrostene(Leaflets) 01-20-one 17(a)-ol-3-one 10.9 5 7.53 6 6.78 5 5.95 10 5.72 10 5.29 7 5.00 8 4.71 9 4.22 4 3.94 2 3.60 3 3.33 4 3.05 7 2.82 1 2.51 1 2.20 2
d , A. 1/11 D4. Ab-Androstene3 (8)-ol-17-one-3-acetate 9.99 8 8 31 3 6.73 8 6.05 3 5.49 3 5.17 10 4.99 2 4.70 2 4.54 10 4.41 6 4.12 6 3.72 7 3.58 4 2.95 5 2.74 4 2.62 4 2.47 4 2.28 1 2.14 1
d , A. 1/11 D5. Androstan3(a)-ol-17-one 11.1 4 8.67 4 7.38 2 6.81 4 6.46 2 5.91 10 5.11 7 4.80 8 4.63 6 4.52 6 4.28 5 4.12 5 3.94 4 3.79 4 3.63 5 3.51 1 3.30 1 3.19 6 3.06 4 2.96 4 2.84 5 2.70 4 2.54 1 2.48 1 2.42 1 2.33 4 2.25 3 2.20 3 2.15 6 1 97 5 1.41 5 1 79 1
d , A. 1/11 d , A. 1/11 D7. 16.17-Epoxy-A6-pregnene3 (p)-ol-20-one-3-aoetate 13.1 2.62 2.50 8.04 2.41 7.53 2.35 7.09 2.28 5.79 2 21 5.01
d , A.
D8. 8.15 7.66 7.00 6.61 6.28 6.06
D6.
d , A. 1/11 Ah'n-Pregnadiene 3 (p)-ol-20-one 12.5 8 10.6 3 8.12 1 6.13 4 5.74 10 5.44 10 5.01 4 4.83 2 4.22 9 4.10 9 3.93 1 3.81 1 3.47 2 3.30 7 3.18 2 3.08 3 2.97 3 2.73 1 2.02 1 1.88 1
1/11 d , A. 1/11 As-Prennene-3(8)-01-20one-3-acetate 2.84 3' 2.71 3 1 2.66 1 2.54 2 2.48 2.41 2
d , A.
1/11
d . A.
1/11
d , A.
1/11
d , A.
1/11
D. Monohydroxy-Monoketones (Continued) D 7 16 17-Epoxy-A5-pregneneD8. A6-Pregnene-3(B)-ol-203(,8)-bl-20-bne-3-acetate (continued) one-3-acetate (continued) 10 2.19 2 5.74 10 2.29 2.12 5.50 10 2.23 3 1 1 2.08 5.16 3 2.17 5 2.02 10 4 4 4.75 2.07 1.95 4.47 2.04 7 1 6 1.90 4.26 2.01 2 3 4 1.85 4.02 3 2 4 1.96 1.77 3.82 2 2 4 1.88 1.62 3.63 2 10 6 1.84 4 1.57 3.41 4 1 3 3 1 1.54 3.29 1.49 2 2 3.21 3 1.32 4 2 2 3.11 2.97 1.23 1 1 3
d , A. 1/11 d , 4. I/Il D9. 17(8)-hIethyl-A4androstene-17(a)-ol-3- D10. Ab-Pregnene-3(p)one -01-20-one-3 methyl ether 12.3 11.9 5 8.39 10.8 6 6.49 9.56 1 6.07 7.06 10 6.09 5.74 10 5.41 4 5.87 5.10 5.64 9 4.71 5.31 9 4.43 5.06 4 4.22 4.76 3 4.48 3.92 9 4.18 3.82 2 3.82 3.70 2 3.67 3.43 2 3.30 3.46 3 3.18 3.24 7 3.06 3.05 3 2.92 2.98 3 2.86 2.74 3 2.71 2.75 3 2.63 3 2.53 2.43 2.50 1 2.38 2.39 8 2.25 2 2.25 2.21 2.19 2 2.04 2.10 1 1.99 2.00 2 1.85 1.96 2 1.78 1.80 1
d, A.
1/11
d , A.
d , A. 1/11 D11. AS-Pregnene3(p),21-diol-20-one-21 acetate 9.77 7 9.03 7 6.66 3 3 6.37 5.97 10 5.72 10 5.17 3 4.85 10 4.28 4 4.15 4 3.97 4 3.66 4 3.51 2 3.29 4 3.00 4 2.82 2 2.69 3 2.56 3 2.38 2 2.36 2 2.20 3 2.09 2 1.98 2 1.89 1
1/11
E. hlonohydroxy-~lonocarboxyacids El. 3(B)-Hydroxy-bisnor-ASE2. 3(p)-Acetoxy-bisnor-A~cholenic acid cholenic acid 3 14.4 13.7 5 2 8.85 -5.97 10 2 7.26 5.75 5 9 5.91 5.55 9 5.25 5.37 10 6 5.08 7 5.03 10 4.fi6 4.82 5 9 4.15 4.68 5 7 4.02 4.53 5 6 4.43 3.76 4 . 3 4.22 1 2 3.53 3.35 4.01 1 3 3.27 3 .a1 4 3 2 3.12 3.72 7 3.01 3 7 3.53 2.92 4 6 3.39 2.69 3.32 5 1 3.14 1 5 2.48 1 4 2.30 3.08 3.01 3 2 2.31 2.14 2.96 2 7 1 2.07 2.86 1 2.78 2 1 1,88 2.68 I 2.62 3 4 2 55 ' 2 2.47 4 2.38 3 2.28 3 2.21 2 2.13 2.06 2 2.00 3 1.91 3 1.82 1 1,74 1
517
V O L U M E 27, N O . 4, A P R I L 1 9 5 5 Table 11. Powder Diffraction Data for Steroids (Continued) d, A.
I/Ii
d , A. I/Ii BILE ACIDS F2. Desoxycholic Acid 6 12.0 8 8.98 2 6.92 10 6.28 3 5.87 3 5.66 7 5.41 3 5.19 6 5.03 3 4.47 4 4.27 6 3.97 4 3.85 5 3.69 3 3.41 3 3.33 4 3.24 2 3.07 1 2.88 2 2.77 1 2.71 3 2.61 3 2.52 4 2.46 1 2.40 1 2.36 2 2.32 1 2.13 2 2.00 2 1.94 2 1.83
d , A.
1/11
F.
F1. Cholic Acid 11.4 9.83 7.94 7.06 6.78 6.49 6.19 5.93 5.74 5.37 5.16 4.94 4.75 4.45 4.24 4.00 3.82 3.69 3.56 3.43 3 31 3.19 3.11 3 02 2.87 2.72 2.64 2.56 2.51 2.46 2.41 2.35 2.24 2.19 2.13 2.06 1.99
6 3 6 2 9 9 1 1 10 2 3 2 3
8 2 5 2 4 4 1 2 3 1 1 1 2 1 4 2 2 2 2
? 1 1
F3.
Dehydrocholic Acid 15.1 5 12.9 4 11.9 2 10.3 5 4 9.61 7.83 1 6.86 1 6.39 4 5.93 5 5.66 10 5.26 7 4.96 7 4.76 1 4.62 3 4.47 6 4.25 5 4.15 6 3.97 4 3.84 2 3.63 2 3.45 4 3.32 3 3.18 4 3.03 3 2.95 3 2.67 2 2.65 2 2.57 2 2.46 2 2.41 1 2.35 2 2.29 1 2.23 2 2.13 2 2.07 2
mortar to a fineness of about 200 mesh. The powders were placed in thin wall plastic tubes of 0.01-mm. wall thickness and 0.2-mm. diameter ( 2 , 3 ) . The mounted samples were exposed to nickel filtered copper radiation produced a t 35 KVP and 20-ma. current for 5 hours in Norelco (North American Philips Co., Inc., Mount Vernon, N. Y . )of 114.59-mm. diameter, Debye-Scherrer cameras. The patterns (Figure 1 ) were recorded on Kodak No-Screen x-ray film, developed for 5 minutes a t 68’ F. in Kodak x-ray developer. Relative intensities ( I / Z l ) of the pattern lines (Table 11) were determined by visual estimation with the strongest line noted as 10. The d values are given in Angstrom units with the copper radiation weighted wavelength value of 1.5418 A. used as the basis of spacing calculations. The wider use of the x-ray method of analysis for organic compounds should supplement melting point determinations and the use of infrared absorption analysis ( 4 ) . A distinct advantage of this method is that very small quantities of sample are requiredone milligram is usually sufficient for an analysis. Visual comparison with standard diffraction patterns usually (Figure 1) has been found sufficient for identification of these steroids, without resort to d value calculation. LITERATURE CITED
(1) Bernal, J. D., Crowfoot, D., and Fankuchen, I., Trans. Roy. Soc. ( L o n d o n ) , 239A, 135 (1940). (2) Beu, K. E., Rev. Sei. Instr., 22,62 (1951). (3) Beu, K. E., and Claasen, H. H., Ibid., 19, 179 (1948).
(4) Dobriner, K., Katzenellenbogen, E. R., and Jones, R. K., “Infrared Absorption Spectra of Steroids,” Interscience, New York, 1953.
RECEIVEDfor review September 16. 1954.
Accepted December 6, 1954.
Infrared Spectra of Alkyl Hydroperoxides HOMER R. WILLIAMS and HARRY S. MOSHER Department of Chemistry, Stanford University, Stanford, Calif.
The infrared spectra of 17 alkyl hydroperoxides, both primary and secondary, have been recorded between 2 and 15 microns. In each case the hydroperoxide showed a characteristic but rather weak absorption in the region 11.4 to 11.8 microns, which has been previously correlated with the oxygen-oxygen stretching vibration. This is a region in which some of the corresponding alcohols also absorb and thus i t is not a unique means of characterizing the hydroperoxide. All primary and secondary alkyl hydroperoxides showed absorption in the 12.0- to 12.5-micron region. A most interesting alternating pattern is shown by normal alkyl hydroperoxides in this region; those which had an even number of carbon atoms (butyl through decyl) showed two maxima (at about 12.1 and 12.4 microns) while the odd-numbered members of the series showed a single maximum at about 12.3 microns.
S
TUDY of the infrared spectra of hydroperoxides has been hindered by lack of sufficient examples of pure members of
this class. The availability of many new primary and secondary alkyl hydroperoxides (9) has permitted a more extensive study than was previously possible ( 3 , 4,7 ) . I n the present study the infrared spectra of nine primary and eight secondary pure liquid alkyl hydroperoxides (9) were recorded in the range 2 to 15 microns. The spectra of the corresponding alcohols were taken in each case for comparison. The important featuree of these spectra are recorded in Tables I to IV and Figures 1 to 7 .
EXPERIMEYTAL
Materials. The spectra were taken in each case on analytically pure (determined by combustion) alkyl hydroperoxides made by the methods outlined previously (9). The samples were used soon after preparation and were stored in the dark and cold until ready for use. The determinations were made without solvent using both a 0.003-inch polyethylene spacer and a thinner film which resulted when no spacer was employed. The spectra for both thicknesses are represented in Figures 1, 2, 3,and 4. Spectral Determinations. All spectra Fere determined on the Perkin-Elmer double beam recording Model 21 infrared spectro-
Table 1. Wave Length of OH Stretching Band of Alkyl Hydroperoxides and Corresponding Alcohols R n-Propyl n-Butyl Isoamyl n-Amvl n-HeGyl n-Heptyl n-Octrl n-Nonyl n-Decyl sec-Butyl Cyclopentyl 2-Pentyl 3-Pentyl %Hexyl 3-Hexyl 2-Heptyl 2-Octyl &Butyl
R-OH, P
2.98 2 99 2.99 2 99 3 on
3.01 3.00 3.02 3.00 2.99 2.98 3.00 2.95 2.96 2.98 2.99 2.90 2.96
R-OOH.
Shift,
P
P
2.94 2.96 2 95 2.96 2 94 2.92 2.96 2.97 2.98 2.96 2.95 2.96 2 90 2.93 2.95 2 98 2.91 2.91
0.04
0.03 0.04 0.03 0.06 0.09 0.04 0.05
0.02 0.03
0.03 0.04 0.05 0.03 0.03 0.01 0.05 0.05
