US2192935A - Esters of polycyclic alcohols and a method of producing the same - Google Patents
Esters of polycyclic alcohols and a method of producing the same Download PDFInfo
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- US2192935A US2192935A US15100A US1510035A US2192935A US 2192935 A US2192935 A US 2192935A US 15100 A US15100 A US 15100A US 1510035 A US1510035 A US 1510035A US 2192935 A US2192935 A US 2192935A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J1/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, not substituted in position 17 beta by a carbon atom, e.g. estrane, androstane
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J75/00—Processes for the preparation of steroids in general
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- This invention relates to esters of polycyclic alcohols and more particularly to esters of the cyclopentano polyhydro phenanthrene series, having. the characteristics of germinal gland hermones, and a method of producing the same.
- esters of polycyclic alcohols with germinal gland hormone characteristics are ob- 10. tained by subjecting acyl derivatives of the following structural formula:
- alkyl or aryl group Y either hydrogen or a hydroxy group
- R. an acyl group to the action 7 of reducing agents capable of hydrogenating the 5 benzene nucleus in the molecule of said starting material into a hydroaromatic nucleus, so as to form compounds of the structural formula:
- the starting materials used for carrying out said hydrogenation process are, for instance, mono-acylated follicle hormone hydrate or mono- 4 acylated dihydro follicle hormone and the like, i. e., compounds having the characteristics of the female sex hormones, whilst the reaction products obtained by the hydrogenation possess the characteristics of the male sex hormones.
- esters of polycyclic alcohols of similar constitu tion having, also the characteristics of the male sex hormones, by reducing in the same manner the esters of the male sex hormones .C19H30O2 and 50 (31032802 and the like compounds as they are obtained, for instance, by the processes of the copenoling U. S. application Serial No. 723,928, filed May 4, 1934 (which. describes a method for the purification of hormones by acylation, sepa- 55 ration of the ester, and subsequent saponification), the German Patents Nos. 576,967 and 583,854 from natural sources, such as urine and the like, or synthetically, for instance, by oxida-. tion of the sterols, such as cholesterol and the like, in which latter case crystalline products will 5 necessarily be obtained. .Thus, when syntheta ically produced estersof androsterone, its isomer,
- acyl compounds may be sub-: jected tothis reducing treatment, but also more or lessimpure preparations which then are puri fied, if required, after reduction has taken place.
- R represents an acyl group
- acylated compounds instead of using the acylated compounds as starting materials, one may proceed in such a manner that the non-acylated compounds are subjected to said reducing treatment under conditions whereby acylation may take place simultaneously.
- the monacyl products obtained may be converted, if desired, into the correspond-. ing diacyl compounds by further acylation of the secondary hydroxy group obtained by the reduction of the keto group.
- reaction products obtained in accordance with the present invention are valuable substances which are either effective physiologically themselves or can be further treated to yield physiologically Valuable materials.
- the mono anddiacetates of androstandiol exhibit a physiological activity in the cock-comb test which is three to four times that of the monoacetate of androsterone; the same is true of the monobenzoate of androstandiol as compared with the monobenzonate of androsterone.
- Example 1 1 g. of 3-acetyl androsterone, obtained accord ing to Example 3 of the German Patent 576,967, is dissolved in 200 cc. of ethanol and, after the addition of the same amount of a previously reduced nickel catalyst, is treated at 170 and 80- 100 atmospheres pressure with hydrogen in an autoclave provided with a stirring device. After about 1 molecule of hydrogen is absorbed, the reaction solution is freed. from the catalyst, whereupon it is evaporated to dryness. A viscous resin is obtained as residue.
- Example 2 sterone are dissolved in 25 cc. of glacial acetic acid and are treated at room-temperature with hydrogen in the presence of 0.5 g. of previously reduced platinum oxide catalyst while shaking or stirring. After absorption of about 1 molecule of hydrogen the hydrogen supplyis interrupted, the
- Example 4 1 g. of the mcnopropionate of the dehydro androsterone is reduced in the same manner as described in Example 3 with hydrogen in the presence of a platinum oxide catalyst, whereby anhydrous propionic acid is usedv as solvent.
- Example 5 l g. of the monobenzoate of dehydro androsterone is mixed with 250 g. of methyl cycl o hexane and is reducedin an autoclave provided with a stirring device at 90-100 C. and a pressure of 20 atmospheres with hydrogen in the Example l g. of the acetate of hydroxy etio allo cholanone (l'l), i. an isomer of androsterone, is dissolved in 50 cc. of 96% alcohol and heated to 60 C. While stirring vigorously an amount of freshly prepared 3% sodium amalgam in excess is added thereto in the course of 1 hour. By adding drop by drop small amounts of acetic acid to this reaction mixture care is taken that the solution is always kept somewhat acid.
- the reaction mixture is heated for a further half hour at 80 C., poured in water and extracted with ether. After shaking with dilute alkali" lye the ethereal extract is evaporatedto dryness whereby the monoacetate of a 3,17-dihydroxy etio allo cholane'is obtained.
- Example 7 11 g. of androsterone is dissolved in 30 cc. of glacial acetic acid and is treated with hydrogen at about 80 C. in the presence of 0.5 g. of a previously reduced platinum oxide catalyst and of 3 cc. of a 48% aqueous hydrobromic acid. After absorption of 1 molecule of hydrogen 10 cc. of acetic acidanhydride are added and the reaction mixture is allowed to stand over night in order w to complete the acetylation. Thereuponit is poured in water and worked up as described in the preceding examples. The diacetate of androstandiol is obtained.
- Example 8 2 g. of androsterone acetate are dissolved in 40- cc. of glacial acetic acid and are reduced with hydrogen at room-temperature in the presence of 1 g. of a platinum oxide catalyst according to Adam-Shriner (see Journ. Am. Chem. Soc., volume 45, page 2171 (1923)). Thereupon the glacial acetic acid is distilled off in a high vacuum at a temperature as low as possible.
- the residue One may'also proceed in such a manner that the diketon'es obtained by the oxidation is then treated with benzoyl chloride in the prespolycyclic alcohols ence of pyridine whereby an isomeric mixture of the 3-acetyl-l'l-benzoyl-androstandiol is obtained.
- esters of the androsterones such as the stearate, the suecinate, the salicylate, the, lactate and the like, into the corresponding esters of the androstandiol, likewise the esters of the dehydro androsterone yield similar androstancliol esters.
- esters of the androsterones such as the stearate, the suecinate, the salicylate, the, lactate and the like
- R represents an acyl group and R reprewherein Rrepresents an acyl group and R represents either hydrogen or an acyl group, comprising subjecting esters of hydroxy ketones of the group consisting of the male sex hormones 'CieHzoOz and Ciel-E802 and their stereo isomers,
- R represents an acyl group and Rrepresents either hydrogen or an acyl group, compris- H OR CwI-IsoOz andCmI-IzaOz and their stereo isomers, to the action of catalytically activated hydrogen in the presence of hydrogenation catalysts so as to transform the keto group in said hydroxy ketones into the secondary alcohol group.
- R. represents an acyl group and R reprecents either. hydrogen or an acyl group, comprising subjecting esters of hydroxy 'ketones of the group consisting of the male sex hormones CisHsoOz and 0191512802 and their stereo isomers, to the action of hydrogen in statu nascendi, so as totransforn the keto group in said hydroxy ketones into the secondary alcohol group.
- R. represents an acyl group and R a member of the group consisting of hydrogen and acyl groups.
- CH2 CH3 CH2 CH3 and having a physiological activity about 3 times as high as that of the corresponding monoacetate of the male sex hormone androsterone.
- R represents an acyl group and R either hydrogen or an acyl group, comprising subjecting' diketones as they are obtained by the-oxidation of the hydroxy ketones of the group consisting of the male sex hormones androsterone CIQHSOOZ and dehydro androsterone 0191-12802 and their stereo isomers, to the action of a reducing agent capable of reducing the keto groups in said diketones into secondary alcohol groups, in
- R. is an acyl group.
- esters of polycyclic alcohols having the formula I wherein R represents an acyl group comprising subjecting the esters of hydroxy ketones of the formula CH3 E Eek/V wherein R represents an acyl group, to the action of reducing agents capable of transforming the keto group into the secondary alcohol group.
- esters of wherein R represents an acyl group comprising on. OH:
- R0 wherein R represents an acyl group, in the presence of an acid to the action of reducing agents capable of transforming the keto group into th secondary alcohol group.
- polycyclic dialcohols comprising subjecting a 3- i ester of a hydroxyketone of the group consisting of the male sex hormones C19H3002 and CmHzaOz' 4 and their stereo isomers, to the action of an agent capable of transforming the keto group in i said hydroxyketones into a secondary alcohol group.
- a method for the production of 3-esters of polycyclic dialcohols comprising subjecting a 3- ester of dehydroandrosterone to the action or agents capable of transforming the keto group in said dehydroandrosterone into a secondary alcohol group.
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Description
Patented a; 12, 1940 UNITED STATES h Fi-leE 3 ESTERS F POLYCYCLIC ALGOHOLS AND A METHOD OF PRODUCENG THE SAME Walter Schoeller, Berlin,Germany, assignor, by
rnesne assignments, to Schering Corporation,
Bloomfield, N. 3., a corporation of New Jersey t No Drawing; ApplieationApril c, 1935, Serial 1 No. 15,100. In Germany April '7, 1934 I This invention relates to esters of polycyclic alcohols and more particularly to esters of the cyclopentano polyhydro phenanthrene series, having. the characteristics of germinal gland hermones, and a method of producing the same.
, In the copencling application Ser'ial No. 7,604, filed February 21,1935, 9. process is described according to which esters of polycyclic alcohols with germinal gland hormone characteristics are ob- 10. tained by subjecting acyl derivatives of the following structural formula:
alkyl or aryl group, Y either hydrogen or a hydroxy group, and R. an acyl group, to the action 7 of reducing agents capable of hydrogenating the 5 benzene nucleus in the molecule of said starting material intoa hydroaromatic nucleus, so as to form compounds of the structural formula:
CH3 X The starting materials used for carrying out said hydrogenation process are, for instance, mono-acylated follicle hormone hydrate or mono- 4 acylated dihydro follicle hormone and the like, i. e., compounds having the characteristics of the female sex hormones, whilst the reaction products obtained by the hydrogenation possess the characteristics of the male sex hormones.
45 Now, it has been found that one can arrive at esters of polycyclic alcohols of similar constitu tion, having, also the characteristics of the male sex hormones, by reducing in the same manner the esters of the male sex hormones .C19H30O2 and 50 (31032802 and the like compounds as they are obtained, for instance, by the processes of the copenoling U. S. application Serial No. 723,928, filed May 4, 1934 (which. describes a method for the purification of hormones by acylation, sepa- 55 ration of the ester, and subsequent saponification), the German Patents Nos. 576,967 and 583,854 from natural sources, such as urine and the like, or synthetically, for instance, by oxida-. tion of the sterols, such as cholesterol and the like, in which latter case crystalline products will 5 necessarily be obtained. .Thus, when syntheta ically produced estersof androsterone, its isomer,
or dehydro-androsterone are employed, as in Examples 3, e, 5, and 6, crystalline hydrogenation products will always be obtained.
Not only the pure acyl compounds may be sub-: jected tothis reducing treatment, but also more or lessimpure preparations which then are puri fied, if required, after reduction has taken place.
Said starting materials. correspond to the followingstructural formulas:
cwnmomo omnlmoio o CH3 CH3:
. on 0 on I o W 5 ll 'l Rik/V QR wherein R represents an acyl group. r
The reduction productsobtaine cl thereby have the following structural formula: l
wherein R represents an acyl group.
l-Iencaby the present invention the keto group groups. For this purpose the starting materials 5.0
are subjected to the action either of catalytically activated hydrogen or of hydrogen in statu nascendi or of atomic hydrogen. The reduction is preferably carried outgin'solution of a suitable solvent. Care must be taken, however, that only the keto group is reduced to the secondary alcohol group without complete reduction to the desoxo product taking place. In the case of the esters of the dehydro androsteron C19H2802, the double bond in ring 2 of the molecule is saturated during the reduction process so that products of the same general formula C19H30(OR) H are obtained from the saturated as well as from the unsaturated starting materials.
Of course, instead of using the acylated compounds as starting materials, one may proceed in such a manner that the non-acylated compounds are subjected to said reducing treatment under conditions whereby acylation may take place simultaneously.
Furthermore, the monacyl products obtained may be converted, if desired, into the correspond-. ing diacyl compounds by further acylation of the secondary hydroxy group obtained by the reduction of the keto group.
The reaction products obtained in accordance with the present invention are valuable substances which are either effective physiologically themselves or can be further treated to yield physiologically Valuable materials. Thus. for example, the mono anddiacetates of androstandiol exhibit a physiological activity in the cock-comb test which is three to four times that of the monoacetate of androsterone; the same is true of the monobenzoate of androstandiol as compared with the monobenzonate of androsterone.
The following examples serve to illustrate the invention, without, however, limiting the same to them.
Example 1 1 g. of 3-acetyl androsterone, obtained accord ing to Example 3 of the German Patent 576,967, is dissolved in 200 cc. of ethanol and, after the addition of the same amount of a previously reduced nickel catalyst, is treated at 170 and 80- 100 atmospheres pressure with hydrogen in an autoclave provided with a stirring device. After about 1 molecule of hydrogen is absorbed, the reaction solution is freed. from the catalyst, whereupon it is evaporated to dryness. A viscous resin is obtained as residue.
Example 2 sterone are dissolved in 25 cc. of glacial acetic acid and are treated at room-temperature with hydrogen in the presence of 0.5 g. of previously reduced platinum oxide catalyst while shaking or stirring. After absorption of about 1 molecule of hydrogen the hydrogen supplyis interrupted, the
catalyst is filtered off, they filtrate is poured in water,-extracted with ether, the ethereal solution is washed free from acid by means of diluted alkali lye and water and the ether is distilled 01f afterdrying. A mixture of isomeric monobenzoic acid esters of the androstandiol remains, which is recrystallized from dilute alcohol.
Example 4 1 g. of the mcnopropionate of the dehydro androsterone is reduced in the same manner as described in Example 3 with hydrogen in the presence of a platinum oxide catalyst, whereby anhydrous propionic acid is usedv as solvent.
After absorption of 2 molecules of hydrogen, on working up according to Example 3, a mixture of isomeric monopropionates of androstandiol is obtained.
' Example 5 l g. of the monobenzoate of dehydro androsterone is mixed with 250 g. of methyl cycl o hexane and is reducedin an autoclave provided with a stirring device at 90-100 C. and a pressure of 20 atmospheres with hydrogen in the Example l g. of the acetate of hydroxy etio allo cholanone (l'l), i. an isomer of androsterone, is dissolved in 50 cc. of 96% alcohol and heated to 60 C. While stirring vigorously an amount of freshly prepared 3% sodium amalgam in excess is added thereto in the course of 1 hour. By adding drop by drop small amounts of acetic acid to this reaction mixture care is taken that the solution is always kept somewhat acid. When the amalgam is added the reaction mixture is heated for a further half hour at 80 C., poured in water and extracted with ether. After shaking with dilute alkali" lye the ethereal extract is evaporatedto dryness whereby the monoacetate of a 3,17-dihydroxy etio allo cholane'is obtained.
. Example 7 11 g. of androsterone is dissolved in 30 cc. of glacial acetic acid and is treated with hydrogen at about 80 C. in the presence of 0.5 g. of a previously reduced platinum oxide catalyst and of 3 cc. of a 48% aqueous hydrobromic acid. After absorption of 1 molecule of hydrogen 10 cc. of acetic acidanhydride are added and the reaction mixture is allowed to stand over night in order w to complete the acetylation. Thereuponit is poured in water and worked up as described in the preceding examples. The diacetate of androstandiol is obtained.
In the same manner there may be obtained from the corresponding monoacyl androsterones in one operation the corresponding diacyl compounds.
of the androsterones, i. e. androstandion and androstendion, are reduced and then acylated to the corresponding diacyl compounds.
Example 8 2 g. of androsterone acetate are dissolved in 40- cc. of glacial acetic acid and are reduced with hydrogen at room-temperature in the presence of 1 g. of a platinum oxide catalyst according to Adam-Shriner (see Journ. Am. Chem. Soc., volume 45, page 2171 (1923)). Thereupon the glacial acetic acid is distilled off in a high vacuum at a temperature as low as possible. The residue One may'also proceed in such a manner that the diketon'es obtained by the oxidation is then treated with benzoyl chloride in the prespolycyclic alcohols ence of pyridine whereby an isomeric mixture of the 3-acetyl-l'l-benzoyl-androstandiol is obtained. r
In a similar manner, there may be transformed other esters of the androsterones, such as the stearate, the suecinate, the salicylate, the, lactate and the like, into the corresponding esters of the androstandiol, likewise the esters of the dehydro androsterone yield similar androstancliol esters. Of course, many variations and changes may i ,be made in the reaction conditions and the starting materials etc. by those skilled in theart in accordance with the principles set forth herein and in the claims annexed hereto. i
What I claim is: i 1. A method for the production of esters of of the general formula C mHiMORlOR and the structural formula:
CH3 CH3 H wherein R represents an acyl group and R reprewherein Rrepresents an acyl group and R represents either hydrogen or an acyl group, comprising subjecting esters of hydroxy ketones of the group consisting of the male sex hormones 'CieHzoOz and Ciel-E802 and their stereo isomers,
to theaction of agents capable of transforming the, keto group insaid hydroxy ketones into the secondary alcohol group, and acylating said secondary alcohol group formed thereby.
3. A method for the production of esters of polycyclic alcohols of the general formula C19Hso C-R OR and the structural formula:
CH CH3 i I I Ro v\/ wherein R represents an acyl group and Rrepresents either hydrogen or an acyl group, compris- H OR CwI-IsoOz andCmI-IzaOz and their stereo isomers, to the action of catalytically activated hydrogen in the presence of hydrogenation catalysts so as to transform the keto group in said hydroxy ketones into the secondary alcohol group.
.4. A method for the production of esters of polycyclic alcohols of the general formula C19H3o(OR)O R" and the structural formula:
wherein R. represents an acyl group and R reprecents either. hydrogen or an acyl group, comprising subjecting esters of hydroxy 'ketones of the group consisting of the male sex hormones CisHsoOz and 0191512802 and their stereo isomers, to the action of hydrogen in statu nascendi, so as totransforn the keto group in said hydroxy ketones into the secondary alcohol group.
5. A method for the production of esters of polycyclic alcohols of the general formula C19H30(OR) OR and the structural formula:
Nth
wherein Rrepresents anacyl group and Rrepresents either hydrogen or an acyl group, comprising in subjecting hydroxyketones of the group consisting of the male sex hormones androsterones .C19H30O2 dehydro androsterone C19H2a02 and their stereo isomers, tothe action of catalytically activated hydrogen in the presence of hydrogenation catalysts and acylating agents so as to transform the keto group in said hydroxy'ketones into the secondary alcohol group whereby simultaneously acylationof the hydroxy groups takes place. i
6. Esters of polycyclic alcohols of the general formula,C19I-I3u,(OR)OR' and the following structural formula:
whereinR. represents an acyl group and R a member of the group consisting of hydrogen and acyl groups.
ingsubjecting esters of hydroxy ketones of the group consisting of the male sex hormones 7; The. monoacetate of an androstandiol of the general formula 019113202, said. monoacetate corresponding to the following structural formula:
CH2 CH3 and having a physiological activity about 3 times as high as that of the corresponding monoacetate of the male sex hormone androsterone.
8. A method for the production of esters of polycyclic alcohols of the general formula C19H3o(OR) OR. and the structural formula:
I iii/V wherein R represents an acyl group and R either hydrogen or an acyl group, comprising subjecting' diketones as they are obtained by the-oxidation of the hydroxy ketones of the group consisting of the male sex hormones androsterone CIQHSOOZ and dehydro androsterone 0191-12802 and their stereo isomers, to the action of a reducing agent capable of reducing the keto groups in said diketones into secondary alcohol groups, in
the presence of acylating agents so as to form the above mentioned diacyl esters of polycyclic alcohols. i e I I -9.v The monoester of an androstandiol having the structural formula CH; OH
where R. is an acyl group.
10. The monoacetate of an androstandiol havpolycyclic alcohols having the formula 11. A method for the production of esters of polycyclic alcohols having the formula I wherein R represents an acyl group, comprising subjecting the esters of hydroxy ketones of the formula CH3 E Eek/V wherein R represents an acyl group, to the action of reducing agents capable of transforming the keto group into the secondary alcohol group.
12. The monoester of an androstandiol having the structural formula wherein R. is an aliphatic acyl group.
13. A method for the production of esters of wherein R represents an acyl group, comprising on. OH:
R0 wherein R represents an acyl group, in the presence of an acid to the action of reducing agents capable of transforming the keto group into th secondary alcohol group.
14. The monoester of an androstandiol having the structural formula CHI Rik J wherein R represents a dicarboxylic organic acid group.
15. Esters of polycyclic alcohols of the general formula C19H3o(OR) OR and the followingstructural formula CH: OR
polycyclic dialcohols comprising subjecting a 3- i ester of a hydroxyketone of the group consisting of the male sex hormones C19H3002 and CmHzaOz' 4 and their stereo isomers, to the action of an agent capable of transforming the keto group in i said hydroxyketones into a secondary alcohol group.
17. A method for the production of 3-esters of polycyclic dialcohols comprising subjecting a 3- ester of dehydroandrosterone to the action or agents capable of transforming the keto group in said dehydroandrosterone into a secondary alcohol group.
WALTER soHoELLER.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2192935X | 1934-04-07 |
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| Publication Number | Publication Date |
|---|---|
| US2192935A true US2192935A (en) | 1940-03-12 |
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ID=7989438
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US15100A Expired - Lifetime US2192935A (en) | 1934-04-07 | 1935-04-06 | Esters of polycyclic alcohols and a method of producing the same |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2484833A (en) * | 1944-07-29 | 1949-10-18 | Glidden Co | 6-alkoxy-i-androstene-17-ols |
| US2940967A (en) * | 1955-07-11 | 1960-06-14 | Synter S A | Process for the preparation of androsterone and intermediates therefor |
| US3053863A (en) * | 1957-09-06 | 1962-09-11 | Lasdon Foundation Inc | 16-oxygenated androstane, 5-androstene and 1, 3, 5(10)-estratriene esters |
| WO2007068434A2 (en) * | 2005-12-13 | 2007-06-21 | Anna Petroni | Medicament based on a monoester of steroids with long chain fatty acids |
-
1935
- 1935-04-06 US US15100A patent/US2192935A/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2484833A (en) * | 1944-07-29 | 1949-10-18 | Glidden Co | 6-alkoxy-i-androstene-17-ols |
| US2940967A (en) * | 1955-07-11 | 1960-06-14 | Synter S A | Process for the preparation of androsterone and intermediates therefor |
| US3053863A (en) * | 1957-09-06 | 1962-09-11 | Lasdon Foundation Inc | 16-oxygenated androstane, 5-androstene and 1, 3, 5(10)-estratriene esters |
| WO2007068434A2 (en) * | 2005-12-13 | 2007-06-21 | Anna Petroni | Medicament based on a monoester of steroids with long chain fatty acids |
| WO2007068434A3 (en) * | 2005-12-13 | 2007-09-07 | Anna Petroni | Medicament based on a monoester of steroids with long chain fatty acids |
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