SU689621A3 - Method of producing d-homosteroids - Google Patents

Description

(54) METHOD OF OBTAINING D-HOMOSTEROIDS

where R, R, Ri and Ri are as defined above

is alkylated or irradiated if desired, to obtain D-homoteroids of the general formula I, where is a lower alkanoyl or benzoyloxy group,

with the subsequent selection of the target product.

The process is preferably carried out in methanol.

The acylation of the 17a-hydroxy groups in a compound of formula I can be carried out, for example, by treatment with an acylating agent — an acyl chloride or an acyl hydride, in the presence of an acid binding agent, for example pyridine or triethylamine, or in the presence of a strong acid catalyst, for example p-toluenesulfonic acid. Non-hydroxyl-containing organic solvents, chlorinated hydrocarbons, e.g. methylene chloride or hydrocarbons, e.g. benzene, are suitable solvents for the acylation. The 17aa-hydroxy17ar-carboxylic acid D-homoteroid corresponding to the compound of formula I can also be converted first to the mixed steroidcarboxylic anhydride followed by acidic or basic treatment (for example, aqueous acetic acid or aqueous pyridine) using the corresponding carboxylic anhydride, resulting in a desired 17aa-acyloxy derivative of the starting hydroxy derivative of formula I.

The replacement of the COOH group by the COOR group can be carried out by treating the free acid with a diazoalkane — diazomethane in ether, or O-alkyl-S, M-dicyclohexylisourea in an aprotic solvent or by reacting an acid salt, for example an alkali salt, with an alkyl halide or sulfate — methyl or ethyl iodide or dimethyl or diethyl sulfate.

The acylation of the R2-oxygruppe contained in the residue can be carried out similarly to the above-described method of acylation of the 17aa-hydroxy groups. The esterified ester carboxyl group can be transesterified by reaction with an appropriate alcohol in the presence of an acidic catalyst, for example perchloric acid. Compounds in which R is an alkyl group substituted by a halogen or hydroxyl group can be prepared if the ester salt of the corresponding homosteroid carboxylic acid is reacted with a sulphonyloxyalkyl halide to form a sulfopyloxyalkyl ester, followed by hydrolysis of the latter in order to prepare the compound with oxyalkyl or by treatment with a halo alkali metal or alkaline earth metal, for example lithium chloride in dimethylformamide, to obtain a haloalkyl in the The R. alkyl halide esters can also be obtained by reacting a D-homoteroid carboxylic acid with an appropriate aldehyde in the presence of a hydrogen halide, preferably in the presence of a catalyst, for example ZnClg.

Example 1. To 950 mg of jD-homohydrocortisone in 47 ml of methanol, 1.42 g of iodic acid in 9.5 ml of water and argon atmosphere are added at room temperature for 4 hours. The reaction mixture is concentrated under reduced pressure until a precipitate forms, approximately 200 ml of water is completely precipitated, filtered, and lll, 17aa-dioxy-3-oxo-1) homo-rostrost-4-one-17ar-carboxylic acid is obtained; T. Il. 274-275 ° C (from alcohol-ether).

UV spectrum: 6242 15300; (with 0.103% vdioxane).

Similarly, receive:

from 9Sb-fluorine - 11p, 17aa, 21 - trioxy -) - homopepgna-l, 4-dien-3,20-dione.

9a-fluoro-11p, 17aa-dioxy-3-oxo-D-romandandrosta-1, 4-diene-17ar-carboxylic acid; mp 273--274 ° C.

UV spectrum: 8239 14900; + 32 ° (with 0.1% in dioxane):

from llp, 17acc, 21 - trioxy - D - homopregna1, 4-diene-3,20-dione.

11 | 3.17aa - dioxy-3-oxo-D-gomoandrosta1; 4-diene-17ar - carboxylic acid; m.p. 237-238 ° C.

UV spectrum: e24z I600;

from 6a-fluoro-11p, 17aa, 21 - trioxy - D-homopregna-1, 4-diene-3,20-dione

6a-fluoro-1 lp, 17aa-dioxy-3-oxo-homo-androst-1, 4-diene-17a | 3-carboxylic acid.

UV spectrum: 243 14900;

from 11p, 17a, 21 - trioxy - ba-methyl-D-roMOpregna-1, 4-diene-3,20-dione

11p, 17a-dioxy-6a-methyl-3-oxCO-Z) - homo-androst-1,4-diene-17ar-carboxylic acid is obtained; m.p. 279-282 ° C.

UV spectrum: 8243 14150; , +43 (with 0.1% in methanol).

Example 2. To a solution of 120 mg llp, 17aadioxy-3-oxo-D-homoandrost-4-ene-17-carboxylic acid and 0.13 ml of triethylamine in 3.1 ml of CH2Cl2 are added dropwise at 0 ° C with 0.88 ml acetyl chloride and stirred for 40 min. The reaction mixture is diluted with methylene chloride and washed with 3% sodium hydrogen carbonate solution, 1N. hydrochloric acid and water, dried and evaporated. The residue was dissolved in 3.1 ml of acetone and 0.1 ml of diethylamine was added. The mixture is concentrated in vacuo, the precipitated precipitate is filtered, dissolved in water, acidified with 2N. hydrochloric acid and extracted with ethyl acetate. After drying and evaporation of the solvent, 17aa - acetoxy-1 lp-hydroxy-3-OKCO-D - homoandrost-4-ene - 17ar - carboxylic acid is obtained; m.p. 167-170 ° C (from acetone-hexane).

UV spectrum: 241 13900; +39 (with 0.1% in dioxane).

Similarly, receive:

from methyl ester 11 (3,17aa-dioxy-3OKCO-Z) - homoapstrost - 4-ene - 17ar - carboxylic acid

17aa-acetoxy-11p-hydroxy-3-oxo-O-homoandrost-4-e-17a methyl ester: | 3-carboxylic acid; m.p. 235-237 ° С (from ether).

UV spectrum: 6242 15750; + 49 ° (with 0.1% in dioxane);

from 9a-fluoro-11p, 17aa-dioxy-3-oxo-1) homo-androst-1,4-diene-17ar-carboxylic acid

17aa-acetoxy-9a - fluorine - Pr - hydroxy-3-oxCO-D - homoandrost - 1,4 - diene - 17ar-carboxylic acid; m.p. 232-234 ° C.

UV spectrum: 8240 15200; + 6 ° (with 0.108% dioxia);

from llp, 17aa - dioxy - 3-oxo - D-homoandrost-1, 4-diene-17ar-carboxylic acid

17ash - acetoxy-1 IP - hydroxy-3-oxo-D-roMO androst - 1,4 - diene-17ar-carboxylic acid; m.p. 251 ° С (with decomposition).

UV spectrum: 6243 14500; (, 1% in methanol);

from 6a-fluoro - llp, 17aa - dioxy - W-oxo-D, growth-1,4 - diene - 17ar - carboxylic acid

17asx - acetoxy-ba - fluoro-Pr - hydroxy-3-cco-D-homoandrost - 1,4 - cie-17ar - carboxylic acid; T. Il. 208 ° С (from acetone - hexane).

UV spectrum: 6243 14650; + 2G (with 0.1% in methanol);

from llp, 17aa - dioxy - 6a - methyl - 3-oxo D - homoandrost - 1,4-diene-17ar - carboxylic acid

17aa-acetoxy-1 IP-hydroxy-6methyl-3-oxo-D-homoandrost-1,4-dien-17ar-carboxylic acid is obtained; m.p. 234-235 ° C.

UV spectrum: 6243 14750; +9 (with 0.1% in DMSO).

Example 3. 50 mg of 11 · 3.17aa-dioxy-3OKCO-D-homoandrost-4-ene-17ar-carboxylic acid was dissolved in 3 ml of methanol and 2.6 ml of 0.06 n was added. ethereal solution of diazomethane at 0 °. After 5 minutes, a few drops of acetic acid were added and the mixture was evaporated. After filtration using 1 g of alumina, methyl 11p is obtained, 17aa - dioxy-3-oxo-D - homoandrost-4-ene-17ar - carboxylic acid; m.p. 186-188 ° C (from ether).

UV spectrum: b24z 15750; + 95 ° (, 1% in dioxane).

Similarly, receive:

from 17aa - acetoxy - Ir - hydroxy - Z-oxo-Ogomoandrost-4-ene-17ar - carboxylic acid

methyl ester 17aa - acetoxy - 11p-hydroxy-3-OKCo-D - homoandrost - 4-ene-17ar - carboxylic acid, so pl. 235-237 ° C (from ether).

UV spectrum: 6 15750; + 49 ° (with 0.1 in dioxane);

from 17ar - acetoxy - 9-fluoro - 1 ip - hydroxy-3OKCO-D - homoandrost - 1,4-dey - 17ar-carboxylic acid

methyl ester 17aa - acetoxp-9-fluoro-hydroxy-3-OKCO-Z) - homoandrosta-1,4-dien17ar - carboxylic acid; m.p. 244-245 ° C.

UV spectrum: 2415; . (with 0.1% in dioxane);

from 17aa-acetoxy-1 IP - hydroxy-3-oxo-D-romoandrost - 1,4 - di- 17ar - carboxylic acid

methyl ester 17oa - acetoxy-1 lp-hydroxy 3-OKCO-Z) - homoandrost - 1,4-diene-17ar-carboxylic acid; m.p. 235-237 ° C.

UV spectrum: 6242 15100; , (with 0.1% in dioxane);

from 17aa - acetoxy-ba - fluoro-Pr-hydroxy-ZOKCO-D - homo-androsta-1,4 - diene-17or-carboxylic acid

methyl ester 17aa - acetoxy-ba-fluoroPr. hydroxy-3-oxo-O-gomoandrosta-1,4-dieneP-carboxylic acid; m.p. 238-239 ° C.

UV spectrum: 6242 15500; + SG (with 0.1% in methanol);

from Pr - hydroxy-3-oxo-17aa - propionyloxy-Z) - homoandrost-4-en-17ar - carboxylic acid

1 ip-hydroxy-3-oxo-17a-apropio-iyloxy-D-methyl ester - homoandrost-4-ene-Parkarboic acid.

UV spectrum: 6241 14900; + 48 ° (from 0.102% in dioxane).

Example 4. To a solution of 3.2 g of Ir, 17-adioxy-3-oxo-D - homoandrost-4-ene - 17-carboxylic acid and 4.2 ml of triethylamine

in 86 ml of CH2Cl2 at 0 ° C under argon atmosphere, 29 ml of propionyl chloride is added dropwise and stirred for 45 minutes. The mixture was poured into cold dilute hydrochloric acid and extracted three times with methylene chloride. The organic solution is washed with saline solution, dried and evaporated. The residue of proponic acid is removed by repeated evaporation with toluene, the MI — hydroxy-3-oxo-17a-apropionyloxy-D — homo-androst-4-ene-17-carboxylic acid is obtained as a foam. UV spectrum: 6241 15000: + 37 ° (with 0.1% in dioxane). Similarly, receive:

from 9a-fluoro-llp, 17aa-dioxy-3-oxo-Z) homo-androsta-1, 4-diene-7a-carboxylic acid

9a - fluorine - IR - hydroxy-3-oxo - 17o-propionyloxy - D - homoandrost - 1.4 -

17cr-carboxylic acid: mp. 221 ° C

UV spectrum: 6240 14500; (with 0.1% in dioxane);

from llp, 17aa - dioxy - 3 - oxo - D - homoandrosta-1, 4-diene - 17ar - carboxylic acid

receive lip - hydroxy-3-oxo - Paa. - iropionyloxy - D - homoandrost - 1,4 - dienPar - carboxylic acid; m.p. 220-22GS.

UV spectrum: 6243 14900; -g6 (with 0.1% in dioxane).

If oily acid chloride or benzoyl chloride is used instead of propionyl chloride, then

from llp, 17aa - dioxy - Z-oxo-D - homoandrost-1, 4 - diene - 17ar - carboxylic acid

17aa-butyryloxy-1 ip-hydroxy-3-oxo-D-mooandrost-1, 4-diene-17ar-carboxylic acid; m.p. 220-22GS.

UV spectrum: 8244 14300; + 5 ° (with 0.1% in dioxane);

from 11p, 17aa - dioxy - 3-oxo-Z) - homoandrosta-1, 4-diene - 17a-p - carboxylic acid

17aa - benzoyloxy - Ir - hydroxy-3-oxo-Dhomoandrosta-1, 4 - di- 17ar-carboxylic acid; m.p. 177-179 ° C.

UV spectrum: 222 20850; , -38 (with 0.1% in dioxane). Example 5. 420 mg of 11 p-hydroxy-3-oxo-1 Taapropionyloxy-Z) - homoandrost - 4-ene-17-carboxylic acid, 0.5 ml of triethylamine and 0.5 ml of n-butyl iodide in 10 ml of acetone kin t 48 h, then poured into ice-cold dilute hydrochloric acid and extracted with CH2Cl2. The organic solution is washed with a solution of sodium chloride, dried and evaporated. Proxy-3-oxo-17aa-propionyloxy-O-homo-androst-4-ene-17ar-carboxylic acid butyl ester is obtained; m.p. 150-151 ° C (from acetone-hexane).

UV spectrum: 6241 16150; + 4G (from 0.104% in dioxane).

Similarly, receive:

from 17aa - acetoxy - Ir - hydroxy-3-oxo-Dhomo-androst-1, 4 - diene-17ar - carboxylic acid and methyl iodide

methyl ester 17aa - acetoxy - 11p-hydroxy-3-OKCo-jD - homoandrost - 1,4-diene-17 -carboxylic acid;

from 17aa - benzoyloxy - lip-hydroxy-3-oxo-d-homoandrost - 1,4 - di- 17ar - carboxylic acid and methyl iodide

17aa-benzoyloxy-Proksp-3-OKCo-D methyl ester - homoandrosta-1,4-diene-17-carboxylic acid; m.p. 152-155 ° C.

UV spectrum: 6232 24 100; -45 ° (with 0.1% in dioxane);

from 17aa - butyryloxy - Pr - hydroxy-3-oxo-D-homoandrost - 1,4 - diene-17ar - carboxylic acid

17aa methyl ester - butyryloxy-1 ipoxy-3-OKCo-D - homoandrost-1,4-diene-17 arrarboxy KHCjjQTW; m.p. 173-174 ° C.

UV spectrum: 8244 14550; {with 0.1% in dioxane);

from Ir - hydroxy-3-oxo - 17a - propionyloxy-homo-androst-1,4-diene-17ar-carboxylic acid

11p-hydroxy-3-oxo-17a-propionyloxy - D - homoandrost - 1,4 - diene 7-carboxylic acid methyl ester; m.p. 94-104 ° C.

UV spectrum: 8244 13800; (with 0.1% in dioxane);

from 17aa - adetoxy - Ir - oxy-ba-methylZ-oxo-D-homoandrost-1, 4-diene - 17ar - carboxylic acid

methyl ester 17aa - acetoxy-Pr - hydroxy-bss - methyl-3-oxo - D - homoandrosta-1,4diene-17-carboxylic acid; m.p. 233- 234 ° C.

UV spectrum: 8243 13700; + 90 ° (with 0.1% in dioxane);

from Pr - oxy-3-oxo - 17aa - nipionilokCH-D - homoandrosta-1,4-diene - 17ar - carboxylic acid and ethnlbromide

11p-hydroxy-3-oxo-17aa-propionyloxy - Z) - homoandrost - 1,4 - diene17aa - carboxylic acid ethyl ester; m.p. 148-149 ° C.

UV spectrum: 8243 14450; : а about 4-17 ° (from 0.1% in dioxane);

of 11 p-hydroxy-3-oxo-17aa-iropionilocCH-D-homoandrost-1,4-diene-17ar-carboxy1OH2 acid and "-butyl iodide

Pr-hydroxy-3-oxo-17a-propionyloxy-D-homo-androsta-1,4-dien-17ar-carboxylic acid butyl ester; m.p. 163-164 ° C.

UV spectrum: 8244 14580; (with 0.1% in dioxane).

Example 6. Analogously to Example 5, 3,11-dioxo-17a-carboxylic acid butyl ester is obtained; m.p. 154-156 ° C (from acetone - hexane).

UV spectrum: 6238 16250; + 77 ° (from 0.103% in dioxane).

Example 7. Analogously to example 3 receive:

methyl ester 17aa - acetoxy - 9a, 11 rdichloro-3-oxo - D - gomoandrost - 4-ene-17 carboxylic acid; m.p. 241 ° C.

UV spectrum: 8240 17100; + 89 ° (with 0.102% in methanol) and

9a-bromo-11p methyl ester - hydroxy-3-oxo-17aa - propionyloxy-D - homoandrost, 1 4-diene-17ar - carboxylic acid; m.p. 171 - 172 ° C.

UV spectrum: 8242 13750; + 53 ° (with 0.1% in dioxane).

Example 8. To 900 mg of 11p-hydroxy-17aa-propionyloxy-3-oxo-D-homoandrost-4-en17ar-carboxylic acid, 3 ml of dimethylformamide was added 0.5 ml of triethylamine and 1 ml of chloroiodomethane and stirred at room temperature. After 24 and 48 hours, another 0.5 ml of triethylamine and 1 ml of chloroiodomethane are added. After 72 hours, it is poured into ice-cold diluted hydrochloric acid, dried and evaporated, Proxy-17aa-propionyloxy-3-oxo-Z) - homo-androst-4-ene-17ar-carboxylic acid methyl ester is isolated by chromatography on silica gel; m.p. 180-181 ° C.

UV spectrum: 8242 17350; ) +82 (with 0.104% in dioxane). Similarly, receive:

pz 11p-hydroxy-3-oxo-17aa-propioyloxy-d-homo-androsta-1,4-diep-17ar-carboxylic acid

1 ip-hydroxy-3-oxo-17ass-propionyloxy-D-homoandrosta-1,4def-17ar-carboxylic acid chloromethyl ester; m.p. 151 -153 ° C.

UV spectrum: 6244 14700; + 56 ° (with 0.1% in dioxane);

from 9a-fluoro - Ir - hydroxy-3-oxo - 17 (over-propionyloxy-D - homoandrosta-1,4-diene-17a (3-carbopic acid

9a-fluoro-1 lp-hydroxy-Zoxo-17aa chlorophenyl ester - propynyloxy-D - homoandrost 1, 4-diene-17ar - carboxylic acid; m.p. 172-173 ° C.

UV spectrum: 6238 15500; + 52 ° (with 0.1% in dioxane).

Example 9. To 500 mg of Pr-hydroxy-17aa-propiopyloxy-3OKCO-D chloromethyl ester, a homoandrost-4-ene-17ar-carboxylic acid in 65 ml of acetonitrile was added 1 g of silver fluoride and stirred. After 3 days, 0.5 g of silver fluoride was added, after another 3 days, the reaction mixture was diluted with ethyl acetate and filtered through silica gel. The eluate is washed with water, dried and evaporated. After chromatography on silica gel, 11 p-hydroxy-17aa-propionyloxy-3-oxo-d-homoandrost-4-ene-17ar-carboxylic acid fluoromethyl ester is obtained; m.p. 171 ° C.

UV spectrum: 8240 23700; + 59 ° (with 0.101% in dioxane).

Similarly obtained from chloromethyl ester Pr - hydroxy-3-oxo-17aa - propionyloxy-D - homoandrosta-1,4 - diene-17ar - carboxylic acid get:

Ir-hydroxy-3-oxo-17a-a-propionyloxy-D-homoandrosta-1,4diene-17-carboxylic acid fluoromethyl ester; m.p. 164-165 ° C.

UV spectrum: 6244 14350; ) + 21 ° (with 0.1% in dioxane);

from chloromethyl 9-fluoro-1 lp-hydroxy-3-oxo-17aa-propionyloxy-D-homoandrosta-1, 4-diene-17ar-carboxylic acid ester

9-fluoro-11p-hydroxy-3oxo-17aa fluoromethyl ester - propionyloxy-1) -homoandrost 1, 4-diene-17ar - carboxylic acid; m.p. 187.5-188 ° C.

UV spectrum: 6239 15 300; + 16 ° (, 1% in dioxane).

Example 10. Analogously to Example 3, pure methyl ester of 17aa-acetoxy-9-chloro-11p-fluoro-3-oxo-D-homoandrost-1, 4-diene-17ar-carboxylic acid is obtained; m.p. 215-216 ° C.

UV spectrum: 8236 15400; + 46 ° (dioxap, 1%).

5 Example 11. Analogously to Example 3, methyl efpr besfluoro-11p-oxy3-oxo-17th is obtained. A - propionyloxy - D - homoandrost-4-ene-17ar-carboxylic acid.

UV spectrum: b234 15900.

10 Example 12. Analogously to Example 3, Pr-hydroxy-3-oxo 17aa-propionyloxy-D-homoandrost-4ene-17ar-carboxylic acid methyl ester is obtained; m.p. 150-151 ° C (acetone-hexane).

15 UV spectrum: 6241 16150; + 41 ° (with 0.1% in dioxane).

Example 13. Analogously to Example 3, 17aa-acetoxy-1 ipoxy-3-oxo-D-homoandrost-4-ene-17ar20 carboxylic acid methyl ester is obtained; m.p. 235-237 ° C (ether).

UV spectrum: S242 15750; , + 49 ° (with 0.1% in dioxane).

Example 14. Analogously to Example 3, 25 are obtained; methyl ester 17aa-acetoxy-1 ipoxy-ba-methyl-3-oxo-1) -homoandrost-4-en17ar-carboxylic acid. UV spectrum: 6242 15000. Example 15. Analogously to Example 3, 17aa is obtained - acetoxy-3,11-dioxo-1) -homoandrost-4-ene-17a; p-carboxylic acid. UV spectrum: 24 16000. Example 16. Under the conditions of Example 1, from 6a, 9-difluoro-llp, 17aa, 21 is trioxy-O-; homo5 pregna-1,4-diene-3,20-d1. It is obtained 6a, 9 difluoro-1 lp, 17aa, 21 - trioxy - () - homoandrosta-1, 4-diene-17ar-carboxylic acid. UV spectrum: b 238 16450. Example 17. Under the conditions of Example 2, from 0 6a, 9-difluoro-11p, 17aa-dioxy-3 -OKCO-Dhomo-androst-1, 4-diene-17ar-carboxylic acid, get 17aa-acetoxy- 6a, 9-difluoro - 1 Ir - hydroxy-3-oxo-gomoandrosta-1,4diene-17ar-carboxylic acid. 5 UV spectrum: 8238 16 300.

Example 18. Under the conditions of Example 3, from 17aa-acetoxy-6a, 9-lifter-1 IP-hydroxy-3oxo-1) homo-androst-1,4-diene-17ar-carboxylic acid, 0 17aa-acetoxy-6a methyl ester is obtained , 9 - difluoro - Pr-hydroxy-Zop: co-D - homoandrosta-1,4-diene - 17ar-carboxylic acid; m.p. 291-292 ° C.

UV spectrum: 6238 16600; (0.1P / o in dioxane). five

Example 19. 600 mg of 17Qa-acetox-L-3-oxy-D-homoandrost-1,4-dien-17A-carboxylic acid, 600 mg of sodium bicarbonate, 1.2 ml of ethyl bromo-acetic acid and 6 ml of M, M-dimethylacetamide stirred at 20 ° C. After 6 hours, 600 mg of sodium bicarbonate and 1.2 ml of bromoacetic acid ethyl ester are added once more and the mixture is stirred for another 15 hours. The reaction mixture is poured into this mixture (Lipp

and the ether solution is washed with cold

2n. hydrochloric acid, water and a saturated solution of common salt are dried and evaporated in vacuo to give 520 mg of ethoxycarbonylmethyl ester 17aaacetox-11 | 3 - hydroxy-3-oxo-D-goluandrosta1, 4-diene-17a | 3-carboxylic acid; m.p. 198--198,5 ° C.

UV spectrum: 8244 15000; +55 (with 0.1% in dioxane).

Example 20. 1.4 g of 17aa - acetoxy-1 ipoxy-3-OKCo-Z) - homoandrost-1,4-diene-17 hydrocarbonic acid, 1.4 g of sodium bicarbonate, 2.8 ml of 2-bromoethanol and 14 ml of N , Ndimethylacetamide is stirred at 60 ° C. After 2 days, esh, e, 1.4 g of sodium carbonate and 2.8 ml of 2-bromoethanol are added. Through

The 3d reaction mixture is cooled and diluted with ether. The ether solution is washed with 2N. cold hydrochloric acid, water and sodium chloride solution, dried and evaporated in vacuo to dryness. After filtration on silica gel, 1.35 g of hydroxyethyl ester 17aa-ethoxy-11 are obtained (3-hydroxy-d-homoandrost-1,4-diene-17ar-carboxylic acid as a foam.

UV spectrum: 8244 13180; (dioxane, with 0.1%).

Example 21. 730 mg of hydroxyethyl ester 17AA - acetoxy-Pr - hydroxy-3-oxo - D-romandandrota-1, 4-diene-17ar - carboxylic acid, 7.3 ml of pyridine and 1.46 ml of acetic anhydride are stirred 0, 25 h at 0 ° C. After adding 10 ml of CH3OH, the reaction mixture is evaporated to dryness in vacuo. After filtration on silica gel, 17aa-acetoxy-Er-hydroxy-3-oxo-D-homoandrost, 1-4-di-17ar-carboxylic acid acetoxyethyl ester is obtained.

UV spectrum: 8243 13880; (with 0.1% in dioxane).

Claims (1)

1. Buhler K., Pearson D. Organic syntheses. Part 2, M., “Peace, 1973, p. 282.