CH343394A - Method of making pregnanals - Google Patents
Method of making pregnanalsInfo
- Publication number
- CH343394A CH343394A CH343394DA CH343394A CH 343394 A CH343394 A CH 343394A CH 343394D A CH343394D A CH 343394DA CH 343394 A CH343394 A CH 343394A
- Authority
- CH
- Switzerland
- Prior art keywords
- oxy
- compounds
- oxo
- free
- pregnan
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- IJFGLPBXLYRFEJ-INGDRISUSA-N (8r,9s,10s,13r,14s,17s)-17-ethyl-10,13-dimethyl-1,2,3,4,5,6,7,8,9,11,12,14,16,17-tetradecahydrocyclopenta[a]phenanthren-15-one Chemical class C1CC2CCCC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1C(=O)C[C@H](CC)[C@@]1(C)CC2 IJFGLPBXLYRFEJ-INGDRISUSA-N 0.000 title description 3
- 238000000034 method Methods 0.000 claims description 8
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims description 6
- 125000004043 oxo group Chemical group O=* 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 239000007858 starting material Substances 0.000 claims description 4
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 150000002832 nitroso derivatives Chemical class 0.000 claims description 3
- PYQMKKXLEOKVIU-JIUSCHCVSA-N C[C@](CC1)([C@@H](CC2)[C@H]3[C@H]1[C@@](C)(CCCC1)C1CC3)[C@H]2C(CN)=O Chemical group C[C@](CC1)([C@@H](CC2)[C@H]3[C@H]1[C@@](C)(CCCC1)C1CC3)[C@H]2C(CN)=O PYQMKKXLEOKVIU-JIUSCHCVSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 claims 1
- 150000003128 pregnanes Chemical class 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- -1 enol esters Chemical class 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- PQSUYGKTWSAVDQ-ZVIOFETBSA-N Aldosterone Chemical compound C([C@@]1([C@@H](C(=O)CO)CC[C@H]1[C@@H]1CC2)C=O)[C@H](O)[C@@H]1[C@]1(C)C2=CC(=O)CC1 PQSUYGKTWSAVDQ-ZVIOFETBSA-N 0.000 description 1
- PQSUYGKTWSAVDQ-UHFFFAOYSA-N Aldosterone Natural products C1CC2C3CCC(C(=O)CO)C3(C=O)CC(O)C2C2(C)C1=CC(=O)CC2 PQSUYGKTWSAVDQ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 description 1
- 241001061127 Thione Species 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003470 adrenal cortex hormone Substances 0.000 description 1
- 229960002478 aldosterone Drugs 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- RBHJBMIOOPYDBQ-UHFFFAOYSA-N carbon dioxide;propan-2-one Chemical compound O=C=O.CC(C)=O RBHJBMIOOPYDBQ-UHFFFAOYSA-N 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002081 enamines Chemical class 0.000 description 1
- 150000002084 enol ethers Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- MDKXBBPLEGPIRI-UHFFFAOYSA-N ethoxyethane;methanol Chemical compound OC.CCOCC MDKXBBPLEGPIRI-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- LGDPTPLJZGPOJL-UHFFFAOYSA-N n,n-dimethyl-2-nitrosoaniline Chemical compound CN(C)C1=CC=CC=C1N=O LGDPTPLJZGPOJL-UHFFFAOYSA-N 0.000 description 1
- SQDFHQJTAWCFIB-UHFFFAOYSA-N n-methylidenehydroxylamine Chemical compound ON=C SQDFHQJTAWCFIB-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- NLRKCXQQSUWLCH-UHFFFAOYSA-N nitrosobenzene Chemical compound O=NC1=CC=CC=C1 NLRKCXQQSUWLCH-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229940107700 pyruvic acid Drugs 0.000 description 1
- 150000007659 semicarbazones Chemical class 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J5/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, substituted in position 17 beta by a chain of two carbon atoms, e.g. pregnane and substituted in position 21 by only one singly bound oxygen atom, i.e. only one oxygen bound to position 21 by a single bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J75/00—Processes for the preparation of steroids in general
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Description
Verfahren zur Herstellung von Pregnanalen Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung von gesättigten und un gesättigten 20-Oxo-pregnan-21-alen, die in den Stel lungen 3 und 18 freie oder geschützte Oxy- oder Oxogruppen enthalten. Als Verbindungen mit ge schützten Oxygruppen kommen z. B.
Ester, Äther, Thioester, Thioäther, Thiol- und Thionester und als solche mit geschützten Oxogruppen Acetale, Mer- captale, Ketale, Enolester, Enoläther und Enamine, Hydrazone, Semicarbazone, Aldehydbisulfitverbin- dungen in Betracht.
Die Verbindungen können weitere Substituenten aufweisen, insbesondere in 11-, ferner in 16- und ioder 17-Stellung eine freie oder funktionell abgewandelte Oxy- oder Oxogruppe. Die Ausgangs stoffe können auch der Homo- und Nor-pregnan- Reihe angehören; insbesondere kann es sich um 19- Nor- undloder D-Homo-pregnane handeln, wobei die Seitenkette sich in 17a-Stellung befindet.
Gemäss der Erfindung lassen sich vor allem auch Verbindungen herstellen, in denen die sterische Anordnung der Sub- stituenten derjenigen in den natürlich vorkommenden Wirkstoffen entspricht, und zwar in Form der Race- mate oder optischen Antipoden, besonders entspre chend substituierte 44-3,20-Dioxo-pregnen-21-ale, in erster Linie das d4-3,18,20-Trioxo-1lss-oxy-pregnen- 21-al bzw. sein 11,18-Cyclohalbacetal.
Die neuen Pregnanale werden erfindungsgemäss erhalten, indem man auf gesättigte oder ungesättigte quaternäre 20-Oxo-pregnan-21-yl-ammonium-verbin- dungen die in 3- und 18-Stellung freie oder ge schützte Oxy- oder Oxogruppen aufweisen, organi sche Nitrosoverbindungen einwirken lässt und aus den erhaltenen Nitronen die Aldehyde in Freiheit setzt.
Dabei verwendet man insbesondere quatemäre Salze, die sich von heterocyclischen Basen aromatischen Charakters, wie Pyridin, Chinolin, Isochinolin, ab leiten.
Diese Ausgangsstoffe werden erhalten durch Umsetzung von tertiären Aminen mit Estern entspre chender 21-Oxy-pregnan-verbindungen und starken anorganischen Säuren, wie Halogenwasserstoffsäuren oder organischen Sulfonsäuren. Die 21-Oxy-pregnan- verbindungen lassen sich z. B. nach den in den schweiz. Patentschriften Nrn. 324896 und 341496 beschriebenen Verfahren herstellen.
Für die Umsetzung mit den quaternären Salzen verwendet man in erster Linie Nitrosoverbindungen der aromatischen Reihe, wie Nitrosobenzol und Di- alkylamino-nitrosobenzole, beispielsweise das p=Di- methylamino-nitrosobenzol. Die Herstellung der Ni- trone erfolgt in Anwesenheit eines alkalischen Mittels.
Es wurde gefunden, dass sich die Kondensation über raschenderweise selbst in Gegenwart von Bicarbo- naten der Alkalimetalle, wie z. B. Kaliumbicarbonat, in ausgezeichneter Ausbeute durchführen lässt. Aus, den Nitronen können die Aldehyde durch Behand lung mit sauren Mitteln in Freiheit gesetzt werden, gegebenenfalls in Gegenwart von Carbonylverbindun- gen. Zum gleichen Ziele gelangt man auch durch Um setzung mit einer Oxocarbonsäure, wie Brenztrauben- säure.
Erfindungsgemäss erhaltene Racemate lassen sich nach an sich bekannten Methoden in die Antipoden spalten.
Die Verfahrensprodukte können als Heilmittel mit der Wirkung von Nebennierenrindenhormonen z. B. des Aldosterons Verwendung finden oder als Zwi schenprodukte zu deren Herstellung dienen.
In dem nachstehenden Beispiel sind die Tempera turen in Celsiusgraden angegeben.
<I>Beispiel</I> Zu einer Lösung von 23 mg rohem 44-3,18,20 Trioxo-llss-oxy-pregnen-21-yl-pyridinium-Salz bzw. dessen 11,18-Halbacetal und 8 mg p-Nitroso-dimethyl- anilin in 1,0 cm3 Methanol und 0,75 cm3 Wasser gibt man 0,25 cm3 0,2-molare wässrige Natriumhydro- gencarbonat-Lösung und lässt nach Einschmelzen im Vakuum 72 Stunden im Dunkeln stehen.
Die Mutter lauge saugt man hierauf ab, wäscht die roten Plätt chen des ausgefallenen (A4-3,18-Dioxo-llss-oxy- ätienoyl)-N-(p-dimethylamino-phenyl)-nitrons bzw. dessen 11,18-Halbacetals mit 40proz. Methanol und Wasser und trocknet im Vakuum über Calcium- chlorid.
17 mg kristallisiertes Nitron werden bei 0 mit 0,5 cm3 äthergesättigter 2-n. Salzsäure 2 Stunden in Stickstoffatmosphäre geschüttelt. Dabei erhält man schliesslich eine nahezu farblose Kristallsuspension. Durch Absaugen, Waschen mit eiskaltem äther gesättigtem Wasser und Trocknen im Vakuum über Calciumchlorid gewinnt man das Hydrat des d4 3,18,20-Trioxo-11 ss-oxy-pregnen-21-als.
Das als Ausgangsmaterial verwendete d-1-3,18,20- Trioxo- l lss-oxy-pregnen-21-yl-pyridinium-Salz bzw. dessen 11,18-Halbacetal kann wie folgt hergestellt werden: 18 mg d4-3,18,20-Trioxo-llss,21-dioxy-pregnen bzw. dessen 11,18-Halbacetal löst man in einer Am pulle in 0,1 cm3 wasserfreiem Pyridin, gibt 18 mg p- Tosylbromid zu und lässt nach Einschmelzen im Vakuum 7 Tage bei Raumtemperatur im Dunkeln stehen.
Die geöffnete Ampulle wird in Aceton-Koh- lendioxyd-Mischung auf -60 bis -70 abgekühlt und das Lösungsmittel durch Sublimation im Hoch vakuum entfernt. Der aufgetaute kristalline Rück stand wird mit wenig Methanol-Äther (3: 1) ver rührt und die Mutterlauge abgesaugt. Die gelblichen Kristalle des d4-3,18,20-Trioxo-llss-oxy-pregnen-21- yl-pyridinium-Salzes bzw. dessen 11,18-Halbacetal werden im Vakuum bei 40 getrocknet.
Process for the production of pregnanals The present invention relates to a process for the production of saturated and unsaturated 20-oxo-pregnan-21-alen which contain free or protected oxy or oxo groups in the 3 and 18 positions. As compounds with ge protected oxy groups come z. B.
Esters, ethers, thioesters, thioethers, thiol and thione esters and, as such with protected oxo groups, acetals, mercaptals, ketals, enol esters, enol ethers and enamines, hydrazones, semicarbazones, aldehyde bisulfite compounds.
The compounds can have further substituents, in particular a free or functionally modified oxy or oxo group in the 11-, also in the 16- and i- or 17-position. The starting materials can also belong to the homo- and nor-pregnancies; in particular it can be 19-nor- and / or D-homo-pregnanes, the side chain being in the 17a position.
According to the invention, it is also possible, above all, to prepare compounds in which the steric arrangement of the substituents corresponds to that in the naturally occurring active ingredients, specifically in the form of the racemates or optical antipodes, particularly correspondingly substituted 44-3,20- Dioxo-pregnen-21-ale, primarily d4-3,18,20-trioxo-1lss-oxy-pregnen-21-al or its 11,18-cyclo-hemiacetal.
The new pregnanals are obtained according to the invention by adding organic nitroso compounds to saturated or unsaturated quaternary 20-oxo-pregnan-21-yl-ammonium compounds which have free or protected oxy or oxo groups in the 3- and 18-positions can act and sets the aldehydes free from the nitrones obtained.
In particular, quaternary salts are used which are derived from heterocyclic bases of an aromatic character, such as pyridine, quinoline, isoquinoline.
These starting materials are obtained by reacting tertiary amines with esters of corresponding 21-oxy-pregnane compounds and strong inorganic acids, such as hydrohalic acids or organic sulfonic acids. The 21-Oxy-pregnan compounds can be z. B. after the in Switzerland. Prepare the methods described in Patent Nos. 324896 and 341496.
For the reaction with the quaternary salts, primarily nitroso compounds of the aromatic series, such as nitrosobenzene and dialkylamino-nitrosobenzenes, for example p = dimethylamino-nitrosobenzene, are used. The nitrones are produced in the presence of an alkaline agent.
It has been found that the condensation surprisingly occurs even in the presence of bicarbonates of the alkali metals, such as. B. potassium bicarbonate, can perform in excellent yield. The aldehydes can be set free from the nitrones by treatment with acidic agents, if appropriate in the presence of carbonyl compounds. The same goal can also be achieved by reaction with an oxocarboxylic acid such as pyruvic acid.
Racemates obtained according to the invention can be split into the antipodes by methods known per se.
The products of the process can be used as remedies with the action of adrenal cortex hormones e.g. B. find the aldosterone use or serve as inter mediate products for their production.
In the example below, the temperatures are given in degrees Celsius.
<I> Example </I> To a solution of 23 mg of crude 44-3,18,20 trioxo-llss-oxy-pregnen-21-yl-pyridinium salt or its 11,18-hemiacetal and 8 mg of p- Nitroso-dimethylaniline in 1.0 cm3 of methanol and 0.75 cm3 of water is added to 0.25 cm3 of 0.2 molar aqueous sodium hydrogen carbonate solution and, after melting, it is left to stand in the dark for 72 hours in vacuo.
The mother liquor is then sucked off, the red platelets of the precipitated (A4-3,18-dioxo-llss-oxyätienoyl) -N- (p-dimethylaminophenyl) -nitrone or its 11,18-hemiacetal was washed with 40 percent Methanol and water and dried in vacuo over calcium chloride.
17 mg of crystallized nitrone are at 0 with 0.5 cm3 of ether-saturated 2-n. Hydrochloric acid shaken in a nitrogen atmosphere for 2 hours. A nearly colorless crystal suspension is finally obtained. The hydrate of d4 3,18,20-trioxo-11 ss-oxy-pregnen-21-als is obtained by suction filtration, washing with ice-cold ether-saturated water and drying in vacuo over calcium chloride.
The d-1-3,18,20-trioxol lss-oxy-pregnen-21-yl-pyridinium salt used as starting material or its 11,18-hemiacetal can be prepared as follows: 18 mg d4-3, 18,20-trioxo-llss, 21-dioxy-pregnene or its 11,18-hemiacetal is dissolved in an ampoule in 0.1 cm3 of anhydrous pyridine, 18 mg of p-tosyl bromide are added and, after melting, left in vacuo for 7 days stand in the dark at room temperature.
The opened ampoule is cooled to -60 to -70 in an acetone-carbon dioxide mixture and the solvent is removed by sublimation in a high vacuum. The thawed crystalline residue is stirred with a little methanol-ether (3: 1) and the mother liquor is filtered off with suction. The yellowish crystals of the d4-3,18,20-trioxo-llss-oxy-pregnen-21-yl-pyridinium salt or its 11,18-hemiacetal are dried at 40 in a vacuum.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH343394T | 1954-02-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH343394A true CH343394A (en) | 1959-12-31 |
Family
ID=4506518
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH343394D CH343394A (en) | 1954-02-05 | 1954-02-05 | Method of making pregnanals |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH343394A (en) |
-
1954
- 1954-02-05 CH CH343394D patent/CH343394A/en unknown
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