Патент USA US2408830код для вставки
Patented ‘Oct. 8, 1946 2,408,829 UNITED STATES PATENT OFFICE 2,408,829‘ ' . ‘ STERGIDAL COMPOUNDS AND METHODS Y 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, 1344, Serial No. 535,753 5 Claims. ' .(Cl. 260—239.5) V l 2 The invention relates to the preparation of new foseudo-sapogenin compounds from steroidal sa jcogenin compounds such as the lilagenin type at about 200° C. for 12 hours. The acetic anhy dricle is removed by distillation and the residue taken up in methanol and the resulting solution treated with decolorizing charcoal and then crystallized from the methanol by concentration and the yuccagenin type described in my copend ing application, Serial No. 535,748, ?led May 15, .1944. The new pseudo compounds are useful as and cooling. The crystals are ?ltered oif and dried to give a product of M. P. 146° C. which also melts at ‘146° C. when mixed with pseudo-yucca intermediates for preparations of physiologically active compounds, such as sex hormones. The reaction by Which steroidal sapogenins are genin triacetate from Example 1. It gives the isomerized to the pseudo-genius have been de 10 correct analysis for C33H4s07 and can be hydro scribed in detail in the copending Patents Nos. lyzed like the triacetate of Example 1 to give 2,352,848 and 2,352,852, issued July 4, 1944. These ‘ pseudo-yuccagenin of M. 'P_ 182° C. ' also include proof of structure of the pseudo The transformations of these examples can be genin side chain. represented as follows: The present invention relates more particularly 15 OHa CH2—CHz to the preparation of pseudo-sapogenin com CH3 013a | / I r pounds by way of isomerization of the corre A CH-—C CHI-CH3 ' sponding sapogenin. The new compounds have \ O—-——C : ‘ H the formula, CH3 CH3 . 20 0:0-01120131 Yl=l\/ 4 H 1 A,O_/\ /W/ H AcO‘L/V ' “ Yuccagenin diacetate 25 on 3 on ‘EH’ /O_—O\H’ 3 /\ \ Where Y and Y’ are members of the class 30 . . oH-o \H — a sum anhydride AcO- N \/\H (e. g. A090) ag?lal'pgt and groups hydrolyzable to OH A O . 35 C Lilagenin diacetate A020 at about 200° 0. i! The invention is illustrated by the following examples. 40 Example 1 CH3 A mixture of 10 grams of yuccagenin diacetate and 15 cc. of acetic anhydride contained in a sealed tube is heated at 200° C. for 10 hours. After removal of the acetic anhydride and treat- 45 A00 merit of a methanol solution of the residue with charcoal (“Norite” brand), the product is then crystallized from methanol to give a product of M. P. lei-145° C. Recrystallization from meth anol raises the melting point to 145—147° C. This The triacetate can be hydrolyzed with dilute alkali, extracted with ether and crystallized from 55 other to give needles of pseudo-yuccagem'n of M, P. i8l-i82° C. Example 2 29 grams of lilagenin diacetate (J. Amer. Chem. Soc. 62, 2620 (1940)) melting at 156° C. and 30 cc. 60 of acetic anhydride are heated in a sealed tube /\ C=O CH——CHa I \ OHnOAc H /\/ \/\H 0 A"°‘\/\/ Pseudo-yuccagenin triacylate (e. g. triacetate) Alkaline l hydrolysis 50 is pseudo-yuccagenin triacetate. Anal; Calc’d for (3331314807! C, 71.2; H, 8.7%. Found: C, 71.5; H, 9.0%. CH3 C CHzCHz CH3 I CH3 CHa | CH3 CHJOHZ /\ C=O (EH-CH3 I \ OHzOH H —O H0_l/\/\l/\/ H H°‘\/\/ Pseudo-yuccagenin (DH-CH3 H 2- CH 2 2,408,829 Whilefor easeyof. manipulation ‘and economy and; organic carboxylic acid ester groups hy the preferred isomerizing agent is acetic anhydride, other lower aliphatic acid anhydrides may drolyzable to 0H also be used. The preferred temperature range < lies between 190° and 200° C. although the reaca 5 tion also takes place as low as 170° or as high as ' , ' H ' 230°. The example is intended as illustrative and the invention is not necessarily limited to the 3. Compounds having the formula, conditions and reactants therein cited. CH, What I claim is: 1. Compounds having the formula, CH; CH; /\ CH: 1 c =C-CHICH! - 15 ~ :1 ' Y’ . Y,_/\/\/ \/\H _ _ . W where Y and Y’ are lower fatty acid ester groups. Y’— 4. Pseudo- My 20 formula, Where Y and Y’ are members of the class OH ' <11 . ' and groups hydrolyzable to " _ if ' > . ' W cca enin tr'ace ate g ‘ 5 W g h t e — 2(‘3112 CH l 2 oHloilc _ , ‘ " l VV '5. Pseudo-yuccagenin having the formula, OH: I A ore-omen, . I _ CH, ‘EH-OH‘ CH, ‘ 35 CH‘ e=o OHSY Y,=/\/\/ \/\H ____ - —\/ I 40 where Y and Y’ are members of the class OH \ /CH2CI;HI oH-cm OH OH H \ ' ha ‘n A A00 ‘ 30 ‘CH: 7 t AcO—/\/\/\/\ 2. Compounds having the formula,_ Y,_ l OH: CH‘ (|J—-C CH CH (EH3 25 <OH CH; CH=Y Y,=/\ F--0 1 (BEECH: O CH=Y . O=O~OHAIJH| —\H . ' (‘m-0H; Y, CH, Hm‘ , l0 ’ EGAN \/ :H l t HO_\/\/ ROMEO B. WAGNER.