CH383356A - Process for the production of new sulfur-containing compounds - Google Patents
Process for the production of new sulfur-containing compoundsInfo
- Publication number
- CH383356A CH383356A CH877660A CH877660A CH383356A CH 383356 A CH383356 A CH 383356A CH 877660 A CH877660 A CH 877660A CH 877660 A CH877660 A CH 877660A CH 383356 A CH383356 A CH 383356A
- Authority
- CH
- Switzerland
- Prior art keywords
- formula
- phenylmercaptomethyl
- benzoic acid
- alkyl ester
- acid alkyl
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 10
- 150000001875 compounds Chemical class 0.000 title description 3
- 238000004519 manufacturing process Methods 0.000 title description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title description 2
- 239000011593 sulfur Substances 0.000 title description 2
- 229910052717 sulfur Inorganic materials 0.000 title description 2
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims description 12
- QXPRAGVOCILNHG-UHFFFAOYSA-N 2-(phenylsulfanylmethyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1CSC1=CC=CC=C1 QXPRAGVOCILNHG-UHFFFAOYSA-N 0.000 claims description 6
- -1 2- (phenylmercaptomethyl) benzoyl halides Chemical class 0.000 claims description 5
- 239000005711 Benzoic acid Substances 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 230000002140 halogenating effect Effects 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 239000007859 condensation product Substances 0.000 claims description 3
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 230000026030 halogenation Effects 0.000 claims 1
- 238000005658 halogenation reaction Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QQOVRPBUAUNBAV-UHFFFAOYSA-N ethyl 2-(chloromethyl)benzoate Chemical compound CCOC(=O)C1=CC=CC=C1CCl QQOVRPBUAUNBAV-UHFFFAOYSA-N 0.000 description 2
- SOUAXOGPALPTTC-UHFFFAOYSA-N ethyl 2-methylbenzoate Chemical compound CCOC(=O)C1=CC=CC=C1C SOUAXOGPALPTTC-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- ZEXQVHUDJCZFCC-UHFFFAOYSA-N 2-(phenylsulfanylmethyl)benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1CSC1=CC=CC=C1 ZEXQVHUDJCZFCC-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002026 chloroform extract Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- PHMZKSHYPLLMSX-UHFFFAOYSA-N ethyl 2-(phenylsulfanylmethyl)benzoate Chemical compound CCOC(=O)C1=CC=CC=C1CSC1=CC=CC=C1 PHMZKSHYPLLMSX-UHFFFAOYSA-N 0.000 description 1
- ZJNVMXXFCNKXLT-UHFFFAOYSA-N ethyl 3-(chloromethyl)benzoate Chemical compound CCOC(=O)C1=CC=CC(CCl)=C1 ZJNVMXXFCNKXLT-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- RZWQDAUIUBVCDD-UHFFFAOYSA-M sodium;benzenethiolate Chemical compound [Na+].[S-]C1=CC=CC=C1 RZWQDAUIUBVCDD-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- HFRXJVQOXRXOPP-UHFFFAOYSA-N thionyl bromide Chemical compound BrS(Br)=O HFRXJVQOXRXOPP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von neuen schwefelhaltigen Verbindungen
Es wurde gefunden, dass man zu neuen 2-(Phenylmercaptomethyl)-benzoylhalogeniden der Formel I (siehe Formelblatt), worin Hal Chlor oder Brom bedeutet, gelangt, indem man einen o-Toluylsäurealkylester der Formel II, worin Alk eine niedere Alkylgruppe bedeutet, mit einem Halogenierungsmittel behandelt, den entstandenen 2-Halogenmethylbenzoesäurealkylester der Formel III, worin Hal Chlor oder Brom bedeutet, mit Thiophenol kondensiert, das Kondensationsprodukt der Formel IV zur 2-(Phenylmercaptomethyl)benzoesäure der Formel V verseift und diese in das entsprechende Säurehalogenid überführt.
Die Ausführung des Verfahrens gestaltet sich beispielsweise wie folgt: Ein o-Toluylsäurealkylester der Formel II, z. B. o-Toluylsäureäthylester, wird mit einem Halogenierungsmittel, vorzugsweise Sulfurylchlorid in Gegenwart von Dibenzoylperoxyd unter Belichten bei erhöhter Temperatur halogeniert.
Der enstandene 2-Halogenmethyl-benzoesäurealkyl- ester der Formel III wird nach Abdampfen des unveränderten Ausgangsmaterials im Hochvakuum destilliert.
Die Kondensation des 2-Halogenmethyl-benzoesäurealkylesters mit Thiophenol erfolgt in Gegenwart der zur Bildung von Natriumthiophenolat berechneten Menge Natronlauge in einem niederen aliphatischen Alkohol, z. B. Athanol, bei erhöhter Temperatur. Nach Entfernen des ausgefallenen Natriumchlorids wird das Lösungsmittel unter vermindertem Druck entfernt, der Rückstand in Chloroform aufgenommen und das Kondensationsprodukt der Formel IV nach bekannten Methoden, z. B. durch Destillation im Hochvakuum isoliert und gereinigt.
Die Gewinnung der 2-(Phenylmercaptomethyl)benzoesäure der Formel V gelingt in üblicher Weise durch Behandeln der Ester der Formel IV mit wässerigen Alkalien bei erhöhter Temperatur in einem aliphatischen Alkohol, z. B. mit wässeriger Natronlauge in Äthanol. Die nach bekannten Methoden isolierte 2-(Phenylmercaptomethyl)-benzoesäure wird anschliessend mit einem Halogenierungsmittel, z. B.
Thionylchlorid oder Thionylbromid, halogeniert, wobei das gewünschte Endprodukt der Formel I erhalten wird.
Die nach dem vorliegenden Verfahren hergestellten, bisher unbekannten 2-(Phenylmercaptomethyl)-benzoylhalogenide zeichnen sich insbesondere durch eine bemerkenswerte insektizide Wirkung aus und sollen deshalb, als Insektenvertilgungsmittel Verwendung finden. Ausserdem können die Verfahrensprodukte auch als Zwischenprodukte zur Herstellung von Medikamenten verwendet werden.
Im nachfolgenden Beispiel, das die Ausführung des Verfahrens erläutert, die Erfindung aber in keiner Weise einschränken soll, erfolgen alle Temperaturangaben in Celsiusgraden; die Schmelz- respektive Siedepunkte sind unkorrigiert.
Formelblatt
EMI1.1
EMI2.1
Beispiel: a) 3-Clzlormethyl-benzoesäureäthylester
100 g o-Toluylsäureäthylester, 107,3 g Sulfurylchlorid und 760 mg Dibenzoylperoxyd werden unter Belichten im Ölbad auf 600 erhitzt. Zur Entfernung von Ausgangsmaterial wird das Reaktionsgemisch nach beendeter Gasentwicklung bei einem Druck von 13 mm Hg mit einer kleinen Raschigkolonne vordestilliert.
Der Rückstand wird mit einer Kolonne bei 0,03 mm Hg destilliert, wobei der 2-Chlormethylbenzoesäureäthylester bei 100-1020 übergeht. b) 2-(Phenylmercaptomethyl)-benzoesäureäthylester
Zu einer Lösung von 48,2 g Thiophenol, 17,5 g Ätznatron in 90 ccm Wasser und 350 ccm Äthanol lässt man 87,0 g 2-Chlormethyl-benzoesäureäthylester zutropfen und erhitzt das Gemisch 75 Minuten am Rückfluss zum Sieden. Nach Abkühlen wird das ausgefallene Natriumchlorid abfiltriert und das Filtrat am Wasserstrahlvakuum eingeengt. Der Rückstand wird in 300 ccm Chloroform aufgenommen, mit 50 ccm eiskalter l-n. Natronlauge ausgeschüttelt, neutral gewaschen und über Magnesiumsulfat getrocknet.
Nach Enfternen des Chloroforms destilliert der 2-(Phenylmercaptomethyl)-benzoesäureäthylester bei 140-1420 bei einem Druck von 0,02 mm Hg. c) 7 -(Phei2ylmeTcaptonZettlyl)-benzoesäure
78 g 2- (Phenylmercaptomethyl) - benzoesäure - äthylester werden in einer Lösung von 13,0 g Atz- natron in 78 ccm Wasser und 53 ccm Äthanol 1 Stunde zum Sieden erhitzt. Anschliessend wird die Reaktionslösung am Vakuum eingeengt, mit 200 ccm Wasser verdünnt und mit 50 ccm Chloroform gewaschen. Die wässerige, alkalische Lösung wird mit 5-n. Salzsäure sauer gestellt und mit 1200 ccm Chloroform extrahiert.
Nach Waschen des Chloroformextraktes mit Wasser und Trocknen über Magnesiumsulfat wird die Lösung etwas eingeengt und mit Petroläther versetzt, wobei die 2-(Phenylmercaptomethyl)-benzoesäure ausfällt, Nach Umkristallisieren aus Chloroform/Petroläther schmilzt die Verbindung bei 111-1130. d) 2-Phenylmercaptornethyl)-benzoylchlond
15 g 2-(Phenylmercaptomethyl)-benzoesäure werden mit 60 g reinem Thionylchlorid 15-20 Minuten auf 60 erhitzt. Das überschüssige Thionylchlorid wird im Vakuum abdestilliert und das 2-(Phenylmercaptomethyl)-benzoylchlorid im Luftbad bei 1 60 und 0,01 mm Hg destilliert.
Process for the production of new sulfur-containing compounds
It has been found that new 2- (phenylmercaptomethyl) benzoyl halides of the formula I (see formula sheet), in which Hal is chlorine or bromine, are obtained by using an o-toluic acid alkyl ester of the formula II in which Alk is a lower alkyl group treated with a halogenating agent, the resulting 2-halomethylbenzoic acid alkyl ester of the formula III, in which Hal is chlorine or bromine, condensed with thiophenol, the condensation product of the formula IV is saponified to form 2- (phenylmercaptomethyl) benzoic acid of the formula V and this is converted into the corresponding acid halide.
The process is carried out, for example, as follows: An alkyl o-toluate of the formula II, e.g. B. o-toluic acid ethyl ester, is halogenated with a halogenating agent, preferably sulfuryl chloride in the presence of dibenzoyl peroxide with exposure to light at elevated temperature.
The resulting 2-halomethyl-benzoic acid alkyl ester of the formula III is distilled in a high vacuum after the unchanged starting material has been evaporated off.
The condensation of the 2-halomethyl-benzoic acid alkyl ester with thiophenol takes place in the presence of the amount of sodium hydroxide solution calculated for the formation of sodium thiophenolate in a lower aliphatic alcohol, e.g. B. ethanol, at an elevated temperature. After removing the precipitated sodium chloride, the solvent is removed under reduced pressure, the residue is taken up in chloroform and the condensation product of the formula IV by known methods, eg. B. isolated and purified by distillation in a high vacuum.
The 2- (phenylmercaptomethyl) benzoic acid of the formula V is obtained in the customary manner by treating the esters of the formula IV with aqueous alkalis at an elevated temperature in an aliphatic alcohol, e.g. B. with aqueous sodium hydroxide solution in ethanol. The isolated by known methods 2- (phenylmercaptomethyl) benzoic acid is then treated with a halogenating agent, for. B.
Thionyl chloride or thionyl bromide, halogenated, the desired end product of the formula I being obtained.
The previously unknown 2- (phenylmercaptomethyl) -benzoyl halides produced by the present process are distinguished in particular by a remarkable insecticidal effect and should therefore be used as insecticides. In addition, the products of the process can also be used as intermediate products in the manufacture of medicaments.
In the following example, which explains the implementation of the method but is not intended to restrict the invention in any way, all temperatures are given in degrees Celsius; the melting and boiling points are uncorrected.
Formula sheet
EMI1.1
EMI2.1
Example: a) 3-Chloromethyl-benzoic acid ethyl ester
100 g of ethyl o-toluate, 107.3 g of sulfuryl chloride and 760 mg of dibenzoyl peroxide are heated to 600 in an oil bath with light. To remove starting material, after the evolution of gas has ended, the reaction mixture is pre-distilled at a pressure of 13 mm Hg using a small Raschig column.
The residue is distilled in a column at 0.03 mm Hg, the 2-chloromethylbenzoic acid ethyl ester passing over at 100-1020. b) ethyl 2- (phenyl mercaptomethyl) benzoate
87.0 g of ethyl 2-chloromethylbenzoate are added dropwise to a solution of 48.2 g of thiophenol, 17.5 g of caustic soda in 90 cc of water and 350 cc of ethanol and the mixture is refluxed for 75 minutes. After cooling, the precipitated sodium chloride is filtered off and the filtrate is concentrated in a water jet vacuum. The residue is taken up in 300 cc of chloroform, with 50 cc of ice-cold l-n. Sodium hydroxide solution extracted, washed neutral and dried over magnesium sulfate.
After removal of the chloroform, the ethyl 2- (phenylmercaptomethyl) -benzoate distills at 140-1420 at a pressure of 0.02 mm Hg. C) 7- (Phei2ylmeTcaptonZettlyl) -benzoic acid
78 g of ethyl 2- (phenylmercaptomethyl) benzoate are heated to the boil for 1 hour in a solution of 13.0 g of caustic soda in 78 cc of water and 53 cc of ethanol. The reaction solution is then concentrated in vacuo, diluted with 200 cc of water and washed with 50 cc of chloroform. The aqueous, alkaline solution is with 5-n. Hydrochloric acid acidified and extracted with 1200 ccm chloroform.
After the chloroform extract has been washed with water and dried over magnesium sulfate, the solution is concentrated slightly and petroleum ether is added, with the 2- (phenylmercaptomethyl) benzoic acid precipitating. After recrystallization from chloroform / petroleum ether, the compound melts at 111-1130. d) 2-Phenylmercaptornethyl) benzoyl chloride
15 g of 2- (phenylmercaptomethyl) benzoic acid are heated to 60 for 15-20 minutes with 60 g of pure thionyl chloride. The excess thionyl chloride is distilled off in vacuo and the 2- (phenylmercaptomethyl) benzoyl chloride is distilled in an air bath at 160 and 0.01 mm Hg.
Claims (1)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH877660A CH383356A (en) | 1960-08-02 | 1960-08-02 | Process for the production of new sulfur-containing compounds |
| OA51508A OA01261A (en) | 1960-08-02 | 1964-12-31 | New derivatives of homothiaxanthene and their preparation. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH877660A CH383356A (en) | 1960-08-02 | 1960-08-02 | Process for the production of new sulfur-containing compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH383356A true CH383356A (en) | 1964-10-31 |
Family
ID=4344607
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH877660A CH383356A (en) | 1960-08-02 | 1960-08-02 | Process for the production of new sulfur-containing compounds |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH383356A (en) |
-
1960
- 1960-08-02 CH CH877660A patent/CH383356A/en unknown
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