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2,408,833 Patented Oct. 8, 1946 UNITED STATES PATENT . OFFICE 2,408,833 METHODS STEROIDAL COMPOUNDS AND SAME FOR OBTAINING THE Romeo B. Wagner, State College, Pa., assignor to Parke, Davis & Company, Detroit, Mich., a cor poration of Michigan No Drawing. Application May 15, 1944, Serial No. 535,757 9 Claims. (Cl. 260—239.5) 1 2 groups. Similarly pseudo-rockagenin has .the allo con?guration at C-5 and hydroxyls at 3, 12 and This invention relates to the preparation of new pseudo-sapogenins from new steroidal sapogenins 27. Pseudo-furcogenin is, however, of the “regu lar” con?guration at C-5 and carries hydroxyls some of which are described in my copending ap plication, Serial No. 530,758, ?led May 15, 19%. at C-3 and 27 with a ketone group at (3-12. (See also J. Am. Chem. Soc. 65, 1199 (1943).) The invention may be illustrated by the follow These compounds are valuable as intermediates ing example: for the preparation of hormones of the sex hor Pseudohecogenin.--A sealed tube containing 5 mone type and particularly of the ‘adrenal cortex g. of hecogenin and 15 cc. .of acetic anhydride was hormone type since they are oxygentated at posi 10 heated at 200° for‘10 hours. The solvent was re tion 12 of the steroid nucleus. moved in vacuo and the solid residue was treated The reaction by which steroidal sapogenins are with a solution of 5 g. of potassium hydroxide in isomerized to. the pseudo-genins have been de 500 cc. ethanol for thirty minutes. The product scribed in detail in the copending Patents Nos. was ether extracted and the ethereal solution was 2,352,848 and 2,352,852,“ issued July 4, 1944. These also include proof of structure of the pseudo genin side chain. This invention relates to the preparation of pseudo-genins having the formula Y’ . CH3 omen, ‘0 DEL A Y”... B washed and evaporated. The acetone solution of the residue after treatment with Norite was con centrated and cooled to give white needles,'M. P. 189-191°; yield 2.6 g. _ Anal.: Calc’d for Cal-14204: C, 75.3; H, 9.8. C, 75.2; H, 9.9. , 20 Found: While for ease of manipulation and economy the preferred isomerizing agent is acetic anhy dride other lower aliphatic acid anhydrides may also be used. The preferred temperature range (Em lies between 190° and 200° C. although the reac 25 tion also takes place as low at 170° or as high as 230°. The example is intended as illustrative and the invention is not necessarily limited to the \ ”\/\/ conditions and reactants therein cited. where Y’ ' is 011 30 The above mentioned transformations can be illustrated diagrammatically as follows: 0 CH5 or a group hydrolyzable to 011 CH; CHr-CH: CH: 2} 11-0 CHI-CH! H where Y’ is a member of the class E OH Hecogenin Acyl anhydride (e. g. acetic anhydride) groups hydrolyzable to on H at 200° 0. for 10 hours 45 and =0 and Y is a member of the class OH and groups hydrolyzable to OH. Speci?c examples of this type compound are pseudo-hecogenin in which Y’ at 3 is OH 50 Y’ at 12 is =0, Y at 27 is —OH, and the con?gu ration at 0-5 is “allo.” In pseudo-hecogenin di acetate both hydroxyls are acylated by acetyl 55 Pseudo hecogenin dlacylate (e. g. diacetate) 2,408,838 lAlkalinehydrolysis 0 CH! CH: CH1 ‘1: _, I Acyl anhydride (0. g. acetic anhydrlde) at 200° 0. for about 10 hours. CHz-CH; =0 \H AN 5 OH-CH: 2 H OH H Ink/m) —\Hl 10 H.011. H1O Ac A00 H Pseudo hecogenin 15 ,7 Pseudo-furcogenin diacylate (e. g. diaeetate) H0 CH . _ ' JlH-C\ (EH-CH; __ o_o§, ' V Alkaline l hydrolysis CH CH: /CH:—CH: a 2° H N V CH; 0 CH: OH; 6 H Ho~ ‘ Id 25 1'1 =C-CH2CH: CHI-CH \H /\ N 1 HQOH H Ho‘k/ \) Rockogem‘n Ac lanh dride (e. . acetic anhydride) l y at 2360" OJm-éeveral hours. 30 Pseudo-Iurcogenin - A00 CH CH (EH: /CH2|CH2 3 ! C=C I \H l /\ In addition to using ethanolic KOH solution for hydrolyzing the acylated pseudogenin to the ‘ CH-CH; 35 2 H . 7 A00 40 4 ' free genin, one can use any other suitable alka-' line solution, for example one containing NaOH, K2CO3, KHCOs, NazCOa, NaHCOa or the like, If an alcohol is required to aid hydrolysis, this can be methanol or other lower aliphatic alcohol in CH 0A0 stead of ethanol. ‘ What I claim is: 1. A pseudo-sapogenin formula is‘: Pseudo-rockogenin triacylate (e. g. triacetate) compound 0; the ‘ 45 1 Alkaline hydrolysis , H0 ,CH 50 CH CH: /CH:CH!_ ’ ' o=o CH-CH: HIOH /\ where Y and Y" are members of the class 55, HOL/I Ylli/ OH <11 ' I’! 60 and groups hydrolyzable to Pseudo-rockogenin CH o CH cm ‘ ' $H_ \ H cm-om CH—CH; 65 and Y’ is a member of the class 0, v _ I, \Hl O_C : /\ 'OH H ‘ 70 and groups hydrolyzable to H0 OH ‘ Furcozenln 2,408,833 5 6 2. A pseudo-sapogenln compound of the for- CH mula' Y’ CHa CH; CHs (IJ / =0 \ v /\ Y, CH CH, z ' o=o-oH,oH1 omen, __ H-CH: |CH=Y \ H 5 H /\ W H Y” Y,,_ 10 "V H-CH: H=Y H i ’\/i H where Y, Y' and Y" are members of the class where Y, Y’ and Y" are each members of the <OH class <0_a°y1 H OH O and H 6. A: pseudo-furcogenm compound or the _ 15 H formula, - v 0 and groupshydrolyzable to 0H: OH’ I OH’ (‘;____.C_CH,CH, OH 20 —"\H H-CH: CH=Y H /\/ \/<; 3. A pseudo-sapcgenln compound of the for mula 25 Y” CH ‘)k Y’ CH a (‘111: 0:0/CH2CH2 H-cm _-'\ Where Y and 1'1Y” are members of the class 0H (Pam (|JH=Y H ____ k 30 and H '7. Pseudo-hecogemn the formula, . havmg . /\/\/ \/\1H Y": 011; 35 where Y and Y" are each members of the class OH 40 H and groups hydrolyzable to 8. Pseudo-rockogenin having the formula, OH HO H CH: C=C-CH:CH: \ and Y’ is a ketone oxygen group. 4. A pseudo-hecogenin compound of the for mulaI O CH: H CH=Y HO- 55 9. Pseudc-furcogenln having the formula, O I tr where Y and Y" are members of the class l I H Y]! H-CH: HQOH V’Y 50 OH; H OH: C==C—CH:CH2 I _—\ (DEF-CH: H CH: CH3 I 60 CH: \Jéi CH-CH: H2011 <02! <0~8CY1 and H H 5. A pseudo-rockogenin compound of the formula, ROMEO B. WAGNER.