DE1069632B - - Google Patents
Info
- Publication number
- DE1069632B DE1069632B DENDAT1069632D DE1069632DA DE1069632B DE 1069632 B DE1069632 B DE 1069632B DE NDAT1069632 D DENDAT1069632 D DE NDAT1069632D DE 1069632D A DE1069632D A DE 1069632DA DE 1069632 B DE1069632 B DE 1069632B
- Authority
- DE
- Germany
- Prior art keywords
- thiodiazole
- alkyl
- aryl
- acid
- thiodiazoles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 150000005840 aryl radicals Chemical class 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 3
- 125000004414 alkyl thio group Chemical group 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000004421 aryl sulphonamide group Chemical group 0.000 claims description 2
- 150000001540 azides Chemical class 0.000 claims description 2
- 125000004475 heteroaralkyl group Chemical group 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- -1 alkoxyl radical Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 6
- 210000004185 liver Anatomy 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- OIWIYLWZIIJNHU-UHFFFAOYSA-N 1-sulfanylpyrazole Chemical group SN1C=CC=N1 OIWIYLWZIIJNHU-UHFFFAOYSA-N 0.000 description 2
- ILKGEOVHANZEFC-UHFFFAOYSA-N 4-ethoxybenzenesulfonamide Chemical compound CCOC1=CC=C(S(N)(=O)=O)C=C1 ILKGEOVHANZEFC-UHFFFAOYSA-N 0.000 description 2
- MSFQEZBRFPAFEX-UHFFFAOYSA-N 4-methoxybenzenesulfonamide Chemical compound COC1=CC=C(S(N)(=O)=O)C=C1 MSFQEZBRFPAFEX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical class C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 1
- XSMOCCOXRCNLRD-UHFFFAOYSA-N 2-sulfanylpyrazol-3-amine Chemical compound Nc1ccnn1S XSMOCCOXRCNLRD-UHFFFAOYSA-N 0.000 description 1
- GJCVWKPGGOMFQR-UHFFFAOYSA-N 4-butoxybenzenesulfonamide Chemical compound CCCCOC1=CC=C(S(N)(=O)=O)C=C1 GJCVWKPGGOMFQR-UHFFFAOYSA-N 0.000 description 1
- DTJVECUKADWGMO-UHFFFAOYSA-N 4-methoxybenzenesulfonyl chloride Chemical compound COC1=CC=C(S(Cl)(=O)=O)C=C1 DTJVECUKADWGMO-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
- C07D285/01—Five-membered rings
- C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
- C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
- C07D285/08—1,2,4-Thiadiazoles; Hydrogenated 1,2,4-thiadiazoles
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
Description
Verfahren zur Herstellung von 5-Arylsulfonamido-1,2,4-thiodiazolen Das Hauptpatent 1057 125 betrifft die Herstellung von 5-Arylsulfonamido-1,2,4-thiodiazolen, die im Arylrest eine oder mehrere niedere Alkylgruppen tragen und in 3-Stellung des Thiodiazolringes durch eine Alkyl-, Alkoxyalkyl-, Alkylmercapto-, Aryl-, Aralkyl-, Heteroaryl- oder Heteroaralkylgruppe substituiert sein können. Diese Verbindungen zeichnen sich durch eine gute Leberschutzwirkung aus, besitzen aber keine unerwünschte bakteriostatische oder blutzuckersenkende Wirkung.Process for the preparation of 5-arylsulfonamido-1,2,4-thiodiazoles The main patent 1057 125 relates to the preparation of 5-arylsulfonamido-1,2,4-thiodiazoles, which carry one or more lower alkyl groups in the aryl radical and are in the 3-position Thiodiazole ring can be substituted by an alkyl, alkoxyalkyl, alkylmercapto, aryl, aralkyl, heteroaryl or heteroaralkyl group. These compounds are distinguished by a good liver protection effect, but have no undesirable bacteriostatic or blood sugar-lowering effect.
Bei weiterer Bearbeitung wurde gefunden, daß solche 5-Arylsulfonamido-1,2,4-thiodiazole, die im Arylrest eine Alkoxygruppe (Alkyl = Methyl bis Butyl) besitzen und in 3-Stellung des Thiodiazolringes durch eine Alkyl-, Alkoxyalkyl-, Alkylmercapto-, Aryl-, Aralkyl-, Heteroaryl- oder Heteroarylalkalgruppe substituiert seinkönnen, ebenfalls eine gute Leberschutzwirkung entfalten.On further processing it was found that such 5-arylsulfonamido-1,2,4-thiodiazoles, which have an alkoxy group (alkyl = methyl to butyl) in the aryl radical and are in the 3-position of the thiodiazole ring by an alkyl, alkoxyalkyl, alkyl mercapto, aryl, aralkyl, Heteroaryl or heteroaryl alkali groups can be substituted, also a good one Develop liver protection effects.
Zur Herstellung der beanspruchten Verbindungen kann man nach den im Hauptpatent beschriebenen Verfahren 5-Halogen-1,2,4-thiodiazole, die in 3-Stellung die genannten Substituenten enthalten, mit Arylsulfonamiden, die im Arylrest eine niedere Alkoxylgruppe (Alkyl = Cl bis C4) tragen, in Form ihrer Salze oder in freier Form in Gegenwart säurebindender Mittel bei erhöhter Temperatur umsetzen oder 5-Amino-1,2,4-thiodiazole, die in 3-Stellung substituiert sein können, mit von Arylsulfohalogeniden oder -aziden, die im Arylrest eine niedere Alkoxylgruppe (Alkyl = Cl bis C4) enthalten, in Gegenwart säurebindender Mittel reagieren lassen. Als Arylsulfohalogenide kommen in erster Linie die Säurechloride in Frage, ferner Säurebromide oder Säurefluoride. Als säurebindende Mittel sind beispielsweise Trialkylamine, Pyridin, Kaliumcarbonat oder Natriumcarbonat geeignet.For the preparation of the claimed compounds can be according to the im Main patent described process 5-halogen-1,2,4-thiodiazole, which in 3-position contain the substituents mentioned, with arylsulfonamides that are in the aryl radical Carry lower alkoxyl groups (alkyl = Cl to C4), in the form of their salts or in free React form in the presence of acid-binding agents at elevated temperature or 5-amino-1,2,4-thiodiazole, which can be substituted in the 3-position by aryl sulfohalides or azides, which contain a lower alkoxyl group (alkyl = Cl to C4) in the aryl radical, in the presence Allow acid binding agents to react. As aryl sulfohalides come first Line the acid chlorides in question, furthermore acid bromides or acid fluorides. As an acid-binding Agents are, for example, trialkylamines, pyridine, potassium carbonate or sodium carbonate suitable.
Die so erhaltenen neuen 5-Alkoxyarylsulfonamido-1,2,4-thiodiazole bewirken im Tierversuch an der durch Tetrachlorkohlenstoff geschädigten Leber der Ratte eine Normalisierung der Leberausscheidungsleistung.The new 5-alkoxyarylsulfonamido-1,2,4-thiodiazoles thus obtained in animal experiments on the liver damaged by carbon tetrachloride Rat normalization of liver excretory capacity.
Beispiel 1 Man suspendiert 34,5g (0,185 Mol) p-Methoxybenzolsulfonsäureamid, 26g wasserfreies Kaliumcarbonat und 2 g Kupferpulver in 200 ccm Diphenyläther. Bei 200'C (Badtemperatur) läßt man langsam unter kräftigem Rühren 25 g (0,185 Mol) 5-Chlor-3-methyl-1,2,4-thiodiazol zutropfen. Nach 5stündigem Rühren wird abgekühlt, der Diphenyläther abdekantiert und der Rückstand in heißem Wasser gelöst. Man filtriert über Kohle, säuert an (pH 4 bis 5) und saugt die kristalline Fällung ab. Nach Umkristallisieren aus 25°/oiger Essigsäure fällt das 5-(4'-Methoxybenzolsulfonamido)-3-methyl-1,2,4-thiodiazol in farblosen Kristallen an, die bei 184,5 bis 185,5°C schmelzen.EXAMPLE 1 34.5 g (0.185 mol) of p-methoxybenzenesulfonic acid amide, 26 g of anhydrous potassium carbonate and 2 g of copper powder are suspended in 200 cc of diphenyl ether. At 200 ° C. (bath temperature), 25 g (0.185 mol) of 5-chloro-3-methyl-1,2,4-thiodiazole are slowly added dropwise with vigorous stirring. After stirring for 5 hours, the mixture is cooled, the diphenyl ether is decanted off and the residue is dissolved in hot water. It is filtered through charcoal, acidified (pH 4 to 5) and the crystalline precipitate is filtered off with suction. After recrystallization from 25% acetic acid, the 5- (4'-methoxybenzenesulfonamido) -3-methyl-1,2,4-thiodiazole is obtained in colorless crystals which melt at 184.5 to 185.5 ° C.
An Stelle von Diphenyläther lassen sich mit demselben Erfolg auch andere hochsiedende, inerte Verdünnungsmittel verwenden, z. B. Diphenyl, Diphenylmethan, Paraffinöl, Dekalin, Tetralin, Methyl- und Chlornaphthaline oder Gemische dieser Verdünnungsmittel.Instead of diphenyl ether can also be used with the same success use other high-boiling, inert diluents, e.g. B. Diphenyl, Diphenylmethane, Paraffin oil, decalin, tetralin, methyl and chloronaphthalenes or mixtures of these Diluents.
Analog erhält man aus p-Äthoxybenzolsulfonsäureamid und 5-Chlor-3-methyl-1,2,4-thiodiazol das 5-(4'-Äthoxybenzolsulfonamido) - 3 - methyl -1,2,4 - thiodiazol, F. 165°C; aus p-Butoxybenzolsulfonsäureamid und 5-Chlor-3-methyl-1,2,4-thiodiazol das 5-(4'-Butoxybenzolsulfonamido)-3-methyl-1,2,4-thiodiazol, F. 178°C; aus p-Methoxybenzolsulfonsäureamid und 5-Chlor-3-äthyl-1,2,4-thiodiazol das 5-(4'-Methoxybenzolsulfonamido)-3-äthyl-1,2,4-thiodiazol, F. 170 bis 171°C; aus p-Äthoxybenzolsulfonsäureamid und 5-Chlor-3-äthyl-1,2,4-thiodiazol das 5-(4'-Äthoxybenzolsulfonamido)-3-äthyl-1,2,4-thiodiazol, F. 152 bis 153°C.Analogously, p-ethoxybenzenesulfonic acid amide and 5-chloro-3-methyl-1,2,4-thiodiazole are obtained 5- (4'-ethoxybenzenesulfonamido) -3-methyl-1,2,4-thiodiazole, mp 165 ° C; the end p-butoxybenzenesulphonic acid amide and 5-chloro-3-methyl-1,2,4-thiodiazole 5- (4'-butoxybenzenesulphonamido) -3-methyl-1,2,4-thiodiazole, Mp 178 ° C; from p-methoxybenzenesulfonic acid amide and 5-chloro-3-ethyl-1,2,4-thiodiazole 5- (4'-methoxybenzenesulfonamido) -3-ethyl-1,2,4-thiodiazole, mp 170 to 171 ° C; 5- (4'-Ethoxybenzenesulfonamido) -3-ethyl-1,2,4-thiodiazole from p-ethoxybenzenesulphonic acid amide and 5-chloro-3-ethyl-1,2,4-thiodiazole, 152 to 153 ° C.
Beispiel 2 Eine Lösung von 11,5 g (0,1 Mol) 5-Amino-3-methyl-1,2,4-thiodiazol in 75 ml Pyridin wird unter Eiskühlung portionsweise mit 20,5 g (0,1 Mol) p-Methoxybenzolsulfochlorid versetzt, 8 Stunden auf 20°C gehalten und 30 Minuten auf 50°C erwärmt. Man dampft das Pyridin im Vakuum ab, digeriert den Rückstand mit 10°/jger Salzsäure, wobei die anfangs ölige Masse langsam kristallin erstarrt. Der Niederschlag wird abgesaugt, in verdünntem wäßrigem Ammoniak gelöst und über Kohle filtriert. Beim Ansäuern (p. 4 bis 5) fällt das 5-(4'-Methoxybenzolsulfonamido )-3-methyl-1,2,4-thiodiazol in Kristallen vom F. 183 bis 184°C an.Example 2 A solution of 11.5 g (0.1 mol) of 5-amino-3-methyl-1,2,4-thiodiazole in 75 ml of pyridine is added portionwise with 20.5 g (0.1 mol) of p-methoxybenzenesulfonyl chloride while cooling with ice added, kept at 20 ° C for 8 hours and heated to 50 ° C for 30 minutes. One steams the pyridine is removed in vacuo, the residue digested with 10 ° / jger hydrochloric acid, with the initially oily mass slowly solidifies in crystalline form. The precipitate is sucked off, dissolved in dilute aqueous ammonia and filtered through charcoal. When acidifying (p. 4 to 5) there is 5- (4'-methoxybenzenesulfonamido) ) -3-methyl-1,2,4-thiodiazole in crystals from mp 183 to 184 ° C.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1069632B true DE1069632B (en) | 1959-11-26 |
Family
ID=594711
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT1069632D Pending DE1069632B (en) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1069632B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3159644A (en) * | 1960-04-11 | 1964-12-01 | Monsanto Co | 3-halo(or nitro)-phenylalkylmercapto-5-halo(or nitro)-1, 2, 4-thiadiazole |
| US4873239A (en) * | 1987-01-29 | 1989-10-10 | Hoechst-Roussel Pharmaceuticals, Inc. | Arylthiadiazolylsulfonamides and derivatives |
-
0
- DE DENDAT1069632D patent/DE1069632B/de active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3159644A (en) * | 1960-04-11 | 1964-12-01 | Monsanto Co | 3-halo(or nitro)-phenylalkylmercapto-5-halo(or nitro)-1, 2, 4-thiadiazole |
| US4873239A (en) * | 1987-01-29 | 1989-10-10 | Hoechst-Roussel Pharmaceuticals, Inc. | Arylthiadiazolylsulfonamides and derivatives |
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