1514
ANALYTICAL CHEMISTRY
results 0.5% too high. With similar treatment, titrations of copper sulfate gave results 0.1 to 1% too high. The lower value for the iron titration can be attributed to hydrolysis, leading to a compensation of errors. Results of titrations almost always gave a positive error, except for those cited in Table IV. I n an attempt to eliminate this error, a series of titrations of copper sulfate with the cuprous iodide system was carried out in a cell enclosed with a light-tight cover; no improvement over results given in Table I11 was discernible. The addition of 1 ml. of 1F sodium nitrate to the cell and subsequent plating of copper, unplating of copper, and production of iodine, demonstrated that nitrate did not react under these conditions. LITERATURE CITED
(1) Arthur, P., Donahue, J. F., ANAL.CHEM.24, 1612 (1952). (2) Cooke, W. D., Furman, N. H., Ibid., 22, 896 (1950).
(3) Keller, R. N., Wycoff, H. D., InoTg. S y n t h y s 2, 1 (1946). (4) Latimer, W. M., "Oxidation Potentials, 2nd ed., p. 186, Prentice-Hall, New York, 1952. (5) Lingane, J. J., Hartley, A. M., Anal. Chim. Acto 11,475 (1954). (6) Lingane, J. J., Iwamoto, R. T., Zbid., 13, 465 (1955). (7) Malmstadt, H. V., Roberts, C. B., ANAL.CHEM.27, 741 (1955). (8) Meier, D. J., Myers, R. J., Swift, E. H., J. Am. Chem. SOC. 71, 2340 (1949). (9) Oelsen, W., Gobbels, P., Stahl u. Eisen 69, 33 (1949). (10) Parsons, J. S., Seaman, W., ANAL.CHEY.27, 210 (1955). (11) Ramsey, W. J., Farrington, P. S., Swift, E. H., Ibid., 22, 332 (1950). (12) Rowley, K., Swift, E. H., Ibid., 26, 373 (1954). (13) Schmid, R. W., Reilley, C. N., Ibid., 28, 520 (1956). (14) Shults, W. D., 11, Thomason, P. F., Kelley, M. T., Ibid., 27, 1750 (1955). (15) Stone, H. W., Ibid., 20, 747 (1948). (16) Ibid., 23, 868 (1951). (17) Swift, E. H., J. Am. Chem. SOC. 51, 2682 (1929). RECEIVED for review April 9, 1956. Acoepted J u n e 25, 1956. Division of Analytical Chemistry, Program in Honor of Ernest H. Swift, 127th Meeting ACS, Cincinnati, Ohio, March-April 1955.
Steroid X-Ray Diffraction Powder Data JONATHAN PARSONS, WILLIAM T. BEHER, and GIZELLA D. BAKER The Edsel B. Ford lnstitute for Medical Research, Henry Ford Hospital, Detroit 2, Mich. X-ray diffraction powder data and powder diffraction photographs for 40 steroids are presented.
is the third in a series of papers presenting x-ray difT H fraction I S powder data and photographs of x-ray diffraction patterns. Including the data in this paper, diffraction patterns
Table I. Patter 11 XU
.AI A2
Index to Steroid X-Ray Diffraction Powder Data M.P. (Uncor.),
Name I. C l ~ STEROIDS e
C.
About 1130 182-184.5
19:3-19,5 1GY-169
C1
C. Trihydric Alcohol 24,24-Di1nethyl-A~-cholene-3(~),20,24-trioI D.
E. El E2 EX E4
F1 F2
F3 F4 F5
F6 a
b
A'-.Androstene-3,17-dione F. Monohydroxymonoketones .Androstane-17(p)-o!-3-one(dihydrotestosterone) A~-Andsostene-3(p)-ol-l7-one-l7-cyanide-3acetate (dehydroepiandrosterone-17-cyanide3-acetatela .Androstane-17(8)-ol-3-one-17-benzoate (dihydrotesterone-17-benzoatei 17(8)-EthynyI-A~-androstene-17(a)-ol-3-one (ethynyl testosterone) A4-Androstene-17-01-3-one-l7-benroate (testosterone benzoate) b Androstane-3(8)-01-17-one (epiandrosterone)
Acetone. Ethanol and ethyl ether.
Dec.
176-177 233-234 194-196
Bischolesteryl etherc
196-199 79- 83
H. Carboalkoxy Acids H I 3(8)-.lcetoxybi~norallocholanicacid H2 3(B)-Hydroxy-A~-cholenicacid H 3 Diacetoxynordeoxyoholic acid H4 3,12-Dihetocholanic acid (dehydrodeoxychohc acid) H 5 3-Formoxy-12-ketocholanic acid H6 3,12-Diformoxycholanic acid (diforniyldeoxycholic acid)
191-191 24&?42 205-207 20&20X 185-186, 5
193-195
I. Carboalkoxy Esters 00- 63 80- 82 92- 97
Diketones
A4-Androstene-3,17-dione Andro~tane-3~17-dione Androstane-3,17-dione-3-enol acetate
SreRoroa (Cont'd.)
ii
G2 i-Cholesterol niethyl etjier
Monoketones
Coprostane-3-one (coprostanone)a A~-Cholestene-3-one (cholestenone) Cliolestane-3-one enol acetate
Cis..
11. BILE Acros . n o BILE ACIDESTERS 148-152
B.5
D1 D2 D3
GI
Dihydric Alcohols
17-Et hyI-A6-andros tene-3,17-dioI .Allopregnane-3(P) ,20(a)-diol-3-acetate AS-.Androstene-3(8) ,17(P)-diol-3-acetate-17benzoate ~5..~ndrostene-3.17-diol-l7-~yanide
~
3Z.P. (;"cor .), C.
hranie i:. Ethers
B1 A~-Androstene-3.17-diol-17-propionate B2 B3 R4
Pattern No.
I.
A. Monohydric Alcohols Esposta-A6,',22-trien-3-01 (ergosterol) Cholestane-3(a)-ol (epicholestanol)
B.
have been reported for 106 steroids. The x-ray diffraction procedure was the same as used in the previous studies ( 1 , 2 ) . The x-ray diffraction method of analysis depends upon each co,mpound's having a characteristic crystallographic structure. There is evidence that some steroids crystallize in two or more polymorphic forms. each with a distinctive x-ray diffraction
106-168 131-133
I1
I5
Metlrj-l 3.12-dihydroxycholanate (methyl deoxycholate) d Methyl 3,12-diacetoxycholanate (methyl diacetyl deoxycholate) d lllethyl diacetylnordeoxycholanate Methyl diacetylbisnordeoxycholate Methyl 3-benzoxy-12-ketocbo1anate
J1 52
111. SAPOGENIX DERIVATIVES Isosarsapogenin acetate fstnilagenin acetate) Kryptogenin acetate
I2 I3 I4
143-147 137-139 175-178
205-209 194-196 282-284 212-214 172-173.5
98-102 5 114-116 152-156 184-167
123 3-12A
151-152 148-150
Iv. S T E R O I D D E R l V h T I Y E S K1 llletliyl hisdeliydsodoisj-nolic acid K2 Seco 3 / / 4 deoxycholic acid (deoxybilianic acid)
231-235 295-298
1 ' . PSEUDOSTEROIDS Meso-3,4-bis(p-hydroxyphenyl)-n-hexane (hexestrol) 3.4-Bis(p-hpdroxyphenyl)-3-hexene (stilbestrol)
182-184 169-170
L1 L2 C
d
Ethyl ether. Methanol.
V O L U M E 28, NO. 10, O C T O B E R 1956
151s
.)..
i
i
I
I
Figure 1. X-ray diffraction powder patterns of steroids.
Key found in Table I
ANALYTICAL CHEMISTRY
1516
d , A.
1/11
I. Cipl~STEBOIDB A.
Monohydric Alcohols
-41. Ergo~ta-A6~7*~'trien-3-01 15.6 0.55 11.9 0.41 9.88 0.41 7.47 0.55 6.92 0.27 5.95 1.00 5.79 0.27 5.45 0.73 5.04 0.27 4.71 0.41 4.52 0.55 4.23 0.05 4.00 0.27 3.85 0.27 3.71 0.27 3.60 0.09 3.52 0.09 3.21 0.09 3.01 0.09 2.83 0.09 2.69 0.18 2.58 0.18 2.38 0.09 2.29 0.05 2.15 0.05 2.14 0.05
A2.
Cholestane3 (a)-ol 16.2 0.11 10.9 0.01 9.88 0.11 8.93 0.03 7.63 0.11 6.92 0.06 6.11 0.20 5.74 0.53 5.26 0.04 4.78 1.00 4.57 0.06 4.05 0.08 3.72 0.08 3.49 0.04 3.30 0.04 3.21 0.06 2.93 0.08 2.53 0.04 2.38 0.08 2.32 0.03 1.98 0.04
B.
d , A,
I/Ii
B2. 17-Ethyl-ASandrostene-3,17-diol 12.0 0.08 10.0 0.03 8.98 0.28 7.14 0.20 6.42 0.20 6.07 1.00 5.75 0.38 5.38 0.56 5.13 0.11 4.91 0.20 4.51 0.11 4.17 0.15 4.04 0.08 3.75 0.15 3.53 0.05 3.36 0.08 3.26 0.08 3.12 0.08 2.93 0.08 2.80 0.11 2.62 0.08 2.49 0.05 2.39 0.05 2.15 0.08 2.09 0.07
B3. Allopregnane3 (8),20(a)-diol-3acetate 12.6 0.06 11.1 0.01 8.76 0.11 7.76 0.04 6.53 0.30 6.12 0.40 5.56 1.00 5.25 0.53 4.37 0.40 4.12 0.08 3.88 0.08 3.54 0.25 3.27 0.11 3.08 0.03 3.00 0.08 2.93 0.08 2.78 0.08 2.57 0.08 2.48 0.06 2.40 0.04 2.31 0.08 2.23 0.08 2.08 0.03 2.03 0.08 1.98 0.03 1.94 0.04 1.85 0.03 1.78 0.04
Dihydric Alcohols
B1.
Ab-Androstene3,17-diol-17propionate 14.5 0.53 10.3 0.13 8.85 0.07 8.04 0.30 7.53 0.40 6.84 0.30 5.85 0.40 5.55 0.73 5.14 0.30 4.62 1.00 4.20 0.07 3.97 0.53 3.81 0.13 3.65 0.18 3.47 0.30 3.37 0.40 3.22 0.13 3.05 0.40 2.89 0.53 2.75 0.07 2.62 0.02 2.56 0.40 2.41 0.13 2.34 0.13 2.31 0.40 2.21 0.40 2.03 0.07 1.98 0.07 1.87 0.07 1.81 0.13 1.60 0.02 1.52 0.02
B4. 9-Androstene3 (p),17(p)-diol-3acetate-17-benzoate 16.7 0.08 9.07 0.01 8.30 0.11 7.31 0.15 5.70 0.73 5.25 0.11 4.78 1.00 4.45 0.53 4.43 0.01 4.04 0.15 3.77 0.06 3.47 0.11 3.23 0.08 3.11 0.08 2.94 0.11 2.84 0.04 2.79 0.04 2.59 0.01 2.41 0.06 2.34 0.06 2.28 0.08 2.24 0.06 2.19 0.04 2.13 0.04 2.09 0.04 2.05 0.04 2.01 0.04 l,95 0.11 1.87 0.01 1.85 0.08 1.76 0.03 1.74 0 03
Table 11. X-Ray Diffraction Powder Data d , A. I/Ii d , h. I/Ii B5. Ab-Androstene3,17-diol-17-cyanide 12.1 0.30 10.2 0.40 8.47 0.30 7.56 0.07 7.03 0.40 6.05 0.53 5.55 1 00 5.31 0 20 LO1 1.00 4.65 0.73 4.32 0.53 3.90 0 53 3.63 0.73 3.50 0.07 3.36 0.40 3.06 0.53 2.87 0.40 2.78 0.07 2.71 0.30 2.53 0.13 2.38 0.40 2.34 0.40 2.25 0.53 2.16 0.40 2.11 0.40 2.06 0.40 2.00 0.20 1.97 0.20 1.91 0.30 1.85 0.03
C.
Trihydric Alcohol
C1. 24,24-DimethylAkholene-3 (8),2024triol 11.7 0.15 9.87 0.10 8.19 0.07 6.89 0.03 6.19 1.00 5.78 0.03 5.47 0.50 5.25 0.37 4.98 0.07 4.64 0.20 4.49 0.27 4.36 0.20 4.20 0.15 3.87 0.20 3.79 0.03 3.43 0.37 3.25 0.03 3.09 0.27 2.84 0.10 2.75 0.20 2.66 0.20 2.58 0.15 2.48 0.10 2.40 0.10 2.35 0.10 2.28 0.20 2.18 0.10 2.14 0.10 2.05 0.15 2.00 0.15 1.93 0.20 1.89 0.02 1.85 0.03 1.80 0.03 1.68 0.03 1.65 0.03
D.
Monoketones
D1. Coprostane-3-one 11.0 0.27 8.43 0.20 6.81 0.37 5.95 1.00 5.25 0.27 4.98 0.27 4.58 0.37 4.22 0.20 4.06 0.20 3.85 0.15 3.69 0.10 3.48 0.10 3.33 0.10 3.22 0.10 3.11 0.03 2.99 0.15 2.88 0.10 2.81 0.03 2.62 0.10
D1. Coprostane-3-one (contd.) 2.50 0.03 2.44 0 03 2 :37 0.07 2 28 2.20 2 10 1 UR 1 S!r
0.02 0.03 0 02 0 OR 0 0:3
~ 4 -lioles c tene-
D2.
3-one 13 7 10 3
7.63 6.89 6.30 5.47 4.80 4.43 4.11 3.93 3.74 3.48 3.31 3.13 2.89 2.77 2.65 2.35 2.31 2.20 2.12 2.05 1.96 1 86 1.82 1.77 1.72 1.68
0.20 0.27 0.02 0.37 0.27 1.00 0.03 0.27 0.20 0.20 0.37 0.07 0.07 0.20 0.10 0.01 0.15 0.15 0.20 0.20 0.20 0.03 0.07 0.01 0.07 0.07 0.03 0.03
D3. Cholestane-3one enol acetate 10.3 0.15 9.45 0.15 8.08 0.11 7.09 0.02 6.22 0.08 5.91 0.11 5.66 0.09 5.40 0.41 4.72 1.00 4.34 0.08 4.16 0.08 4.01 0.11 3.74 0.08 3.51 0.10 3.31 0.08 3,14 0.11 3.00 0.09 2.90 0.09 2.60 0.02 2.46 0.02 2.32 0.05 2.27 0 04 2.13 0.05 2.09 0.05 1.98 0.02 1.89 0.04
E.
El.
Diketones
Ai-Androstene3,17-dione 7.11 0.20 6.76 0.04 6.03 1.00 5.54 0.17 5.16 0.55 4.68 0.04 4.46 0.05 4.24 0.41 4.04 0.08 3.65 0.04 3.55 0.15 3.20 0.11 3.00 0.11 2.80 0.15 2.52 0.11 2.45 0.11 2.36 0.04
d , .A.
El.
I/II
Ad-Androstene3,17-dione (contd.) 2 27 0 08 2 27 0 05 2 12 0 12 2 08 0 04 2 03 0 05 2 00 0 05 1 95 0 04
d , A.
E4.
El.
.Androstane3,174one 10 9 0.13 9 06 0.02 6.42 0.49 6.03 0.27 5.42 1.00 4.94 0.67 4.70 0.20 4.30 0.13 3.87 0.13 3.60 0.13 3.47 0.09 3.37 0.09 3.29 0.09 3.06 0.09 2.98 0.20 2.86 0.36 2.77 0.04 2.69 0.04 2.58 0.36 2.52 0.13 2.34 0.13 2.32 0.20 2.25 0.04 2.17 0.13 2.14 0.13 2.03 0.09 2.00 0.09 1.91 0.13 1.88 0.18 1.84 0.02 1.80 0.01
E3. Androstane3,17-dione-3-enol acetate 11.2 0.30 9.02 0.01 7.90 0.03 6.86 0.01 6.24 0.63 5.40 1.00 4.94 0.53 4.48 0.08 4.14 0.30 3.87 0.15 3.74 0.11 3.56 0.30 3.32 0.08 3.22 0.20 3.04 0.25 3.82 0.11 2.69 0.06 2.62 0.06 2.55 0.06 2.44 0.04 2.35 0.04 2 28 0.11 2.24 0.15 2.19 0.03 2.12 0.06 2.04 0.08 1.97 0.03 1.95 0.04 1.89 0.04 1.83 0.04
Al-.hdrostene3,17-dione 13.8 0.28 7.53 0.05 6.94 0.11 6.39 1.00 5.88 0.01 5.35 1.00 4.93 0.38 4.75 1.00 4.55 0.20 4.24 0.38 3.83 0.15 3.65 0.08 3.55 0.11 3.46 0.11 3.27 0.20
F1.
I/Ii
AI-Androstene3,17-dione (contd.) 3.06 0.56 2.90 0.56 2.81 0.03 2.67 0.15 2.51 0.20 2.43 0.15 2.24 0.03 2.19 0.03 2.12 0.11 2.03 0.03 1.99 0.05 1.92 0.11 1.79 0.08 1.75 0.08
Monohydroxymonoketones
F1. Androstane17(p)-01-3-one 7.94 0.04 6.86 0.11 6.13 1.00 5,68 0.73 5,26 0.20 4.62 0.73
4.03 4 .42 3.82 3.70 3.13 3.01 2.90 2.77 2.70 2.59 2.45 2.34 2.26 2.21 2.10 1.99 1.85 1.82 1.75 1.71
0.2 35 0 0.25 0.20 0.30 0.27 0.15 0.06 0.06 0.08 0.08 0.11 0.11 0.15 0.08 0.03 0.08 0.03 0.03 0.06
F2. As-hndrostene3 (p)-ol-17-one-17cyanide-3-acetate 14.7 0.10 10.4 0.20 7.28 0.27 5.59 0.20 5.20 1.00 4.68 0.37 4.37 0.03 4.20 0.03 3.92 0.20 3.56 0.20 3.43 0.10 3.31 0.10 3.16 0.15 3.00 0.15 2.90 0.03 2.78 0.20 2.50 0.03 2.41 0.15 2.34 0.15 2.27 0.03 2.17 0.20 2.11 0.02 2.04 0.20 1.96 0.07 1.91 0.07 1.88 0.02 1.76 0.07 1.69 0.07
E4.
173. Androstane17(p)-ol-3-one-17benzoate 11 3 0.07 9.07 0.53 8.35 0.13 6.54 0.30 6.11 0.30 5.77 0.40 5.41 1.00 5.11 0.53 4.72 0.53 4.50 0.40 4 22 0.40 3.90 0.30
V O L U M E 28, NO. 10, O C T O B E R 1 9 5 6
1517
Table I1, X-Ray Diffraction Powder Data (COI n tinued) d , .A.
I/Ii
F3. .indrostane17 (8)-01-3-one-I 7benzoate (contd.) 3.67 0 30 .3.44 0 40 3.28 0.13 3.11 0.20 .3.01 0.20 2.81 0 13 2.77 0.13 2.69 0 13 2.54 0 13 2.44 0.13 2.34 0.13 2.31 0 13 2.13 0.30 2.0; 0.20 1.99 0.20 1.90 0.20 1.84 0 20 1.81 0 13 1.73 0.03 1.65 0.02 1.56 0.02 1 49 0 02 1.36 0 03
d , A.
E'6. Androstane3 (p)-ol-17-one 10.4
6.79 6 01 5 74 5 42 5.16
4 .5l 4.19
0.23
410 379 3 .i3 3.38 3 28 311 3 01' 292 2 8" 2.67
25i 2.18 238 2.25 2 09 2.03 1.94 1. 8 0 1 78 1 72 1 ti3
I' 4. 17lp)-EthynylAi-androstene17(u)-ol-3-one 6.24 1.00 5 95 0.56 5 40 0.47 5.02 1.00 4.67 0.94 4 16 0.15 4.02 0.28 3.85 0.11 3.67 0.15 3.50 0.28 3.41 0.08 3 28 0.05 3.18 0.20 3.02 0.20 2.86 0.20 2.71 0.15 2.51 0.15 2.46 0.15 2.42 0.11 2.34 0.03 2.19 0.11 2.11 0.03 2.07 0.03 2.05 0.05 2.00 0.11 1.96 0.11 1.93 0.08 1 83 0.05 1.81 0.05 1.75 0.05 1.62 0.04 1.51 0.03
14-Androstene1i-ol-3-one-17benzoate 13.9 0.38 10.5 0.56 8.0-1 0.56 6.89 0.38 6.46 0.25 6.08 1.00 5.66 1 00 5.23 1 00 4.95 0.56 4.51 0.56 4.42 0 56 4.12 0 38 3.94 0 2.5 :3.79 0.38 3.68 0.25 3.53 0.38 3.36 0.38 3.20 0.38 3.08 0.38 2.92 0.03 2.81 0.56 2.61 0.13 2.45 0.38 2.37 0.13 2.33 0.06 2.27 0.13 2.11 0.25 2.05 0.25 1.99 0.38 1 89 0.13 1 82 0 03
0 ,38 0.25 1.00 1.00 0 25
0.56 0.56 0.38
4 80
C;,
d , A.
1/11
0.23 0.03 0.25 0.25
0.25 0.56 0 06 01:j 0.13 0 06 O.O:? 0.06 0.2.5
0.13 0 OR 0 25 0 ox 0 26 0.03 0.03 0 06
H.
Carboalkosy .Icids
H1. 3(/3)-.Icetoxybisnorallocholariic acid 14 7 0 27 9 GO 0 02 7 69 0 27 6 .56 0 IO 5.96 1.00 5 64 0 15 5.22 0 01 4.95 0.50 4 70 0 27 4 40 0 02 4 13 0 13 3.87 0.20 3.74 0 20 3 GO 0.20 3 44 0 Ii 3.28 0 20 3 16 0 01 3.04 0 li 2,:s 0 10 2 ,a 0 01 2 65 0.01 2 57 0 1.5 2 47 0 10 2.34 0 10 2.28 2.19 2.14 2 04 1 94 1.85 1 63
01.5 0 13 0.10 0 03 0 03 0 01 0 01
G 1.
F5.
G2. i-Choles terol methyl ether 14.7 0.10 10.4 0.27 7.50 0.20 6.84 0.15 6,l5 0.27 5.37 1.00 LO7 0.27 4.46 0.37 4.30 0.20 3.79 0.20 3.58 0.20 3.40 0.20 3 25 0.1; 3.09 0.20 2.93 0.01 2.84 0.01 2.65 0.10 2.57 0.03 2.49 0.07 2.40 0.01 2.31 0.01 2.26 0.10 2.21 0.10 2.16 0.10 2.08 0.20 1.97 0.10 1.89 0.07 1.76 0.01 1.70 0.01 1.63 0.01
H3.
BILE .ICID E3TERS
Ether-
Riscliolesteryl ether 11.0 0 41 8.76 0 15 8,l5 0.15 5.88 0.27 5 47 1.00 5.17 0.27 4.78 0.11 4.60 0.11 4.15 0.15 4.01 0.15 3.77 0.11 3.31 0.02 3.17 0 05 3.09 0.08 2.97 0.11 2.84 0.05 2.70 0 08 2.51 0.05 2.16 0.02 2.04 0.02
d , -4.
1/11
BILE ACIDSA N D
11.
H2, 3(3)-Hydrosy->S. cholenic acid 14 0 0 20 7 20 0 11 6 01 0 I1 5 68 0 87 4 87 1 00 4 40 0 15 406 0 15 3 86 0 15 3 69 0 15 3 52 0 08 3 32 0 05 3 16 0 20 2 98 0 15 2 89 0 38 2 74 0 11 2 55 0 03 2 45 0 11 2 42 0 11 2 38 0 05 2 21 0 03 2 19 0 05 2 os 0 11 2 04 0 08 1 98 0 11 1 89 0 05 1 85 0 05 1 83 0 03
H3.
Diaoetoxynordeoxycholic acid 13.3 0.05 11.0 0.27 7.56 1.00 7.05 0.27 6.24 0.73 5.81 0.18 5,47 0.27 5.19 0.18 4.91 0.27 4.78 0.88 4.60 0 73 4.42 0.37 4.10 0.18 3.94 0.55 3.78 0.55 3.61 0.18 3.48 0.18 3.38 0.27 3.24 0.09 3.16 0.18 3.07 0.09 2.92 0.18
1/11
Diacetoxynordeoxycholic acid (contd.) 2.82 0 05 2.73 0 27 2 6.5 0.0.5 2 r,l 0 05 2 55 0.05 2 50 0 05 2 43 0.27 2.31 0.27 9 " 3
005
2 'I 2 1.5
0 0 0 0 0
2.08 2.04 1 9.; 1 83 1.68 1 64
27 Ob
09 18 05
0.05 0.02 0 02
114. 3.19-Diketocholnnic acid
12.9 8 63 6 22 5.87 5.42 5 1.3 4 Si 4.72 3 54 3 2.5 3 09 2 88 2.4.5 233
0.27 0 03 1.00 0.50 0.50 0 37 0.07 0.75 0 20 0.03 0.02 0 03 0.05 0.07
H5. 3-Formoxy-12ketocholanic acid 8.:(3 0.49 ti.81 0.20 ii.51 100 ii.01 0.20 5.74 0.27 5 52 0 09 ;08 0.67 4.73 0.67 4 :I 0.67 4.35 0.01 $08 0.49 ., 85 0 36 7.68 0.36 3 33 0.36 3 40 0.36 3 25 0.36 3.14 0.27 3 04 0.27 2 96 0.36 2 76 0.36 2 65 0.27 2.58 0.27
:,;;
2.31 2.23 2.15 2 06 1 99 1 94 1.88 1.84 1.69 1.63 1.5.5 1.52
HO.
0.20 0.13 0.13 0.27 0.02 0.01 0.27 0.27 0.09 0.09 0 02 0.02
3,lZ-Diformoxycholanic acid 12.8 0.04 9.82 0.27 7.20 0.55 6.61 0.20 5.89 1.00 5.44 0.41 5.17 0.41 4.89 0.86 4.59 0.41 4.31 0.27 4.10 0.20 3.91 0.20 3.76 0.55 3.56 0.20 3.35 0.02 3.20 0.20 3.09 0.15 2.96 0.20 2 85 0.11 2.71 0 11 2 62 0.15 2 45 0.18 2 29 0.20
d , 4.
1/11
I. Carboalkory Esters
11. Methyl 3.12dihydroxyc holanate 12.1 9.61 8.84 8.04 7.20 6.68 6 07 5.45 4.89 4.51 4.32 4.03 3.85 3.59 3.40 3.23 2.52 2.45
0.09 0.13 0.13 0.49 0.36 0.09 0.43 1.00 0.83 0.09 0.43 0.15
0.20 0.27 0.20 0.24 0.13 0.09
12. Methyl 3,12diacetoxycholanace 14.0 0.05 10.3 0.15 7.38 0.56 6.54 0.20 6.07 1.00 5.59 0.20 5.14 0.65 4.80 0.20 4.41 0.28 4.06 0.38 3.73 0 20 3 53 0 11 3 37 0 08 3 18 0 08 3 04 0 11 2 89 0 11 2 77 0.11 2.69 0.08 2.55 0.11 2.40 0.15 2.27 0.14 2.18 0.08 2.13 0.08 2 05 0.11
13. Methyl diacetylnordeoxycholanate 11.2 0.55 9.35 0.73 8.55 0.09 7 63 1.00 7.00 0.41 6.30 0.55 5.81 0.73 5.57 0.73 4.97 0.86 4.65 0.73 4.46 0.27 4 27 0.27 4.11 0.55 3.90 0.55 3.66 0.09 3.52 0.18 3.44 0.55 3.25 0.41 3.16 0.41 3.01 0.27 2.91 0.05 2.81 0.05 2.74 0.41 2.59 0.05 2.56 0.41 2.48 0.41 2.40 0.05 2.33 0.18 2.29 0.18 2.21 0 05 2.13 0.41 2.06 0.18 2.02 0.18 1.97 0.18 1.93 0.18 1.89 0.27 1.83 0.05 1.72 0.05
d , .4~
I/li
14. Methyl diacetylbisnordeoxycholate 9.87 0.44 8 71 0 7.i 8.22 0.08 7.59 0.32 6 86 0.33 6.17 0.90 5.68 0.75 5.47 0.44 5.17 0 44 4.90 0.32 4 78 0.50 4 55 1.00 4 3.3 0.75 8 78 0.44 3 58 0.08 3 50 0.08 3 35 0.18 3 19 0.18 3 08 0.12 2 94 0.12 2.50 0.12 2.36 0.12 2.30 0.08 2.25 0.18 2 21 0.04 2 16 0.04 2 11 0.12
15. hIethyl3-benzoxy12-ketocholanate 11 9 0 20 11 0 0 55 9 51 0 41 8 19 0 713 6 92 0 27 6 37 0 20 5 55 1 00 5 25 0 41 4 71 0 73 4 46 0 64 4 04 0 41 3 73 0 55 3 58 0 20 3 44 0 27 3 26 0 20 3 09 0 20 2 96 0 15 2 79 0 18 2 61 0 18 2 49 0 15 2 36 0 20 2 26 0 27 2 18 0 20 2 08 0 15 1 99 0 18 I 89 0 15
III. QAPOQENIS DERIV.&TIVES
J 1. Isosarsapogenin acetate 14 7 0 07 13 1 0 15 11 8 0 03 10 8 0 20 9 41 0 03 7 97 0 10 7 28 0 20 7 02 0 75 6 51 0 50 6 15 1 00 5 70 0 67 5 33 0 75 5 02 0 92 4 81 0 50 4 67 0 50 4 41 0 10 4 30 0 I5 4 15 0 03 3 75 0 27 3 51 0 15 3 I9 0 10 3 02 0 10 2 76 0 02 2 61 0 03 2 47 0 02 2 34 0 03
ANALYTICAL CHEMISTRY
1518 Table 11. d , A.
d , A.
1/11
52.
Kryptogenin acetate n 19 15.2 ". 14.0 0.04 0.09 9.07 0.17 7.90 0.20 7.03 1.00 6.21 0.13 5.87 1.00 5.52 4.94 0.13 4.71 0.01 4.38 0.13 4.17 0.83 0.20 3.92 0.27 3.72 0.27 3.50 3.34 0.09 3.25 0.09 0.13 3.08 0.09 2.97 0.04 2.85 0.13 2.77 0.02 2.68 2.56 0.01 2.46 0.09 2.37 0.20 2.29 0.09 2.23 0.04 2.17 0.02 0.01 2.11 0.09 2.07
1/11
52.
Kryptogenin acetate (contd.) 1.97 0.02 1.93 0.02 1.85 0.02 1.80 0.02 1.75 0.02
1"
IV. STEROID DERIVATIVES
K1. Methyl bisdehydroisynolic acid
X-Ray Diffraction Powder Data (Continued) d , .1.
1/11
K1. Methyl bisdehydroissnolic acid (contd.) 3.92 0.32 3.81 0.28 3.63 0.32 3.60 0.28 3.47 0.32 3.33 0.11 3.03 0.20 2.92 0.11 2.79 0.08 2.65 0.11 2.59 0.05 2.53 0.08 2.37 0.15 2.33 0.05 2.24 0.05 2.13 0.11 2.08 0.03 1.99 0.08
Ii2. Sec? 8/(4 deoxycholic acid 9.72 0.47 7.22 0.15 6.49 0.75 5.88 0.56
power pattern. At average room temperature, the particular form of crystal that appears generally depends upon the solvent from which the compound is recrystallized. In presenting the diffraction data of this paper, the recrystallizing solvents and also the resulting melting points for each steroid are specified. Before obtaining their x-ray diffractions, all of the steroids were recrystallized from various solvents. The method of recrystallization was as follows: A sample of the compound was dissolved in a minimum volume of solvent while being heated on a steam bath. Water was then added until the solution became cloudy. While this solution was maintained a t boiling temperature, a sufficient amount of solvent was added to redissolve the precipitate. The compound was allowed to crystallize a t room temperature. I n those cases where the above method failed to yield satisfactory results, ethyl ether was used to enhance the solubility
d , A.
1/11
d. A.
:{,!d"
$ ~ ~ x s c ~ ~ v.PSEE;DO ~ ~ (contd.) 5.57 0.75 5.31 0.08 5.10 1.00 4.90 0.38 4.47 0.38 4.20 0.47 3.88 0.15 3.73 0.38 3.56 0.28 3.41 0.28 3.23 0.11 3.14 0.33 2.97 0.15 2.88 0.05 2.80 0.05 2.70 0.15 2.65 0.05 2.54 0.05 2.50 0.15 2.44 0.08 2.34 0.11 2.28 0.15 2.17 0.15 2.12 0.03 2.07 0.05 2.03 0.05
1/11
STEROIDS
L1. Mes+3.4-bis(phydroxyphenyl). n-hexane
d . A.
1/11
L2. 3,4-Bis(p-hydroxyphenyl)3-hexene 9.41 0.15 8.23 0.11 7.47 0.27 5.85 0.55 5.26 0.02 4.85 1.00 4.45 0.73 4.21 0.20 3.95 0.27 3.74 0.11 3.55 0.34 3.42 0.41 3.16 0.04 3.06 0.04 2.91 0.24 2.56 0.11 2.51 0.15 2.40 0.05 2.31 0.05 2.25 0.02 2.19 0.15 2.04 0.02 1.95 0.04 0.05 1.88 1.84 0.08 1.76 0.08 1.68 0.02 1.65 Q.02 1.60 0.02 1.56 0.04
of the steroid. The substance was then allowed to crystallize from this solution, The solvents used were ethanol, methanol, acetone, and ether. The majority of the steroids were recrystallized from ethyl alcohol. The exceptions are noted in Table I. ACKNOWLEDGMENT
The technical assistance of Rachel Silas and Kathleen Matheson, who assisted in the preparation of the x-ray data, is gratefully acknowledged. LITERATURE CITED (1) Beher, W. T., Parsons, J., Baker, G. D., ANAL.CHEM.27, 1569
(1955). (2) Parsons, J., Beher, W. T., Ibid.,27, 514 (1955). RECEIVEDfor review September 24, 1955. Accepted June 4, 1956.
A System for the Rapid Reduction of Mass Spectrometric Data B. K. FRITTS
and
C . GORDON PEATTIE'
Exploration and Production Research Division, Shell Development Co., Houston, rex.
A system is described which represents a material improvement over the conventional method of reducing mass spectra by manual measurement of peak heights with a ruler. Spectra of compounds of high molecular weight are reduced about six times faster than previously, with no loss of accuracy and without operator fatigue. The data are presented in a form suitable for processing by electronic computers. Use of this system should encourage development of new high molecular weight methods by permitting reduction of spectra in a quantity which would be impracticable by the manual method.
T
HE rapid and accurate measurement of peak heights has
always been a problem in mass spectrometry. Manual measurement has been most widely used; the peak height is read from a ruler laid on the spectrum or by use of grid lines provided on the record. Most workers use a ruler graduated in fiftieths or hundredths of an inch. The deflection is then recorded on the record or on a separate paper together with the galvanometer factor by which it is to be multiplied. Elaborate variations have only increased the time of measurement and have done little to reduce the high fatigue factor. While analyses were limited t o 'Present address. General Electrodynamics Corp., Garland, Tex.
