DE860949C - Process for the preparation of new derivatives of 1, 2, 4-triazine - Google Patents
Process for the preparation of new derivatives of 1, 2, 4-triazineInfo
- Publication number
- DE860949C DE860949C DEG6671A DEG0006671A DE860949C DE 860949 C DE860949 C DE 860949C DE G6671 A DEG6671 A DE G6671A DE G0006671 A DEG0006671 A DE G0006671A DE 860949 C DE860949 C DE 860949C
- Authority
- DE
- Germany
- Prior art keywords
- acid
- triazine
- glyoxylic acid
- preparation
- thienyl
- 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.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title claims description 4
- 150000003920 1,2,4-triazines Chemical class 0.000 title description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229940042396 direct acting antivirals thiosemicarbazones Drugs 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 4
- 150000003584 thiosemicarbazones Chemical class 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002168 alkylating agent Substances 0.000 claims description 3
- 230000002152 alkylating effect Effects 0.000 claims description 3
- 239000012435 aralkylating agent Substances 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims 1
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 9
- -1 5-methylfuryl Chemical group 0.000 description 8
- 229940107700 pyruvic acid Drugs 0.000 description 6
- 150000004716 alpha keto acids Chemical class 0.000 description 5
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 4
- 125000001544 thienyl group Chemical group 0.000 description 4
- 150000003583 thiosemicarbazides Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000001041 indolyl group Chemical group 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 125000002541 furyl group Chemical group 0.000 description 2
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- UIGWHMHFJHXQQM-UHFFFAOYSA-N 1-amino-1-phenylthiourea Chemical compound NC(=S)N(N)C1=CC=CC=C1 UIGWHMHFJHXQQM-UHFFFAOYSA-N 0.000 description 1
- SUKUNUQYDORCFO-UHFFFAOYSA-N 1-amino-3-(furan-2-ylmethyl)thiourea Chemical compound NNC(=S)NCC1=CC=CO1 SUKUNUQYDORCFO-UHFFFAOYSA-N 0.000 description 1
- SKYYTGUCWARUCL-UHFFFAOYSA-N 1-amino-3-ethylthiourea Chemical compound CCNC(=S)NN SKYYTGUCWARUCL-UHFFFAOYSA-N 0.000 description 1
- NAMYKGVDVNBCFQ-UHFFFAOYSA-N 2-bromopropane Chemical compound CC(C)Br NAMYKGVDVNBCFQ-UHFFFAOYSA-N 0.000 description 1
- OPMLSSIBXGDUAE-UHFFFAOYSA-O CC([S+]=C(N)NN)=O Chemical compound CC([S+]=C(N)NN)=O OPMLSSIBXGDUAE-UHFFFAOYSA-O 0.000 description 1
- BEBPHOREGFHVKV-UHFFFAOYSA-N CCN(C(N)=[S+]CC1=CC=CC=C1)N Chemical compound CCN(C(N)=[S+]CC1=CC=CC=C1)N BEBPHOREGFHVKV-UHFFFAOYSA-N 0.000 description 1
- ZQPGBUUUZGYYRW-UHFFFAOYSA-N CCNC(NN)=[S+]CC Chemical compound CCNC(NN)=[S+]CC ZQPGBUUUZGYYRW-UHFFFAOYSA-N 0.000 description 1
- HLTAIJXTVYLUBB-UHFFFAOYSA-N NC(NN)=[S+]CC1=CC=CC=C1 Chemical compound NC(NN)=[S+]CC1=CC=CC=C1 HLTAIJXTVYLUBB-UHFFFAOYSA-N 0.000 description 1
- 125000000066 S-methyl group Chemical group [H]C([H])([H])S* 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- 229940008406 diethyl sulfate Drugs 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- DBPFRRFGLYGEJI-UHFFFAOYSA-N ethyl glyoxylate Chemical compound CCOC(=O)C=O DBPFRRFGLYGEJI-UHFFFAOYSA-N 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 150000002540 isothiocyanates Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000008164 mustard oil Substances 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- RRLOOYQHUHGIRJ-UHFFFAOYSA-M sodium;ethyl sulfate Chemical compound [Na+].CCOS([O-])(=O)=O RRLOOYQHUHGIRJ-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001806 thionaphthenyl group Chemical group 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D253/00—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00
- C07D253/02—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00 not condensed with other rings
- C07D253/06—1,2,4-Triazines
- C07D253/065—1,2,4-Triazines having three double bonds between ring members or between ring members and non-ring members
- C07D253/07—1,2,4-Triazines having three double bonds between ring members or between ring members and non-ring members with hetero atoms, or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D253/075—Two hetero atoms, in positions 3 and 5
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
Erteilt auf Grund des Ersten Oberleitungsgesetzes vom 8. Juli 1949Issued on the basis of the First Overhead Line Act of July 8, 1949
(WiGBl. S. 175)(WiGBl. P. 175)
BUNDESREPUBLIK DEUTSCHLANDFEDERAL REPUBLIC OF GERMANY
DEUTSCHES PATENTAMTGERMAN PATENT OFFICE
KLASSE 12p GRUPPE 10CLASS 12p GROUP 10
G 66ji IVc/12 pG 66ji IVc / 12 p
AUSGEGEBENAM 29. DEZEMBER 1952ISSUED DECEMBER 29, 1952
Dr. Rudolf Hagenbach, und Dr, Hans Gysin, Basel (Schweiz)Dr. Rudolf Hagenbach, and Dr, Hans Gysin, Basel (Switzerland)
sind als Erfinder genannt wordenhave been named as inventors
Verfahren zur Herstellung von neuen Derivaten des 1,2,4-Triazins Patentiert im Gebiet der Bundesrepublik Deutschland vom 1. August 1951 anProcess for the preparation of new derivatives of 1,2,4-triazine Patented in the territory of the Federal Republic of Germany from August 1, 1951
Patentanmeldung bekanntgemacht am 8. Mai 1952Patent application published May 8, 1952
Patenterteilung bekanntgemacht am 6. November 1952Patent issued November 6, 1952
Die Priorität der Anmeldung in der Schweiz vom 1. August 1950 ist in Anspruch genommenThe priority of the registration in Switzerland from August 1, 1950 has been claimed
D erivate des ι, 2, 4-Triazins der allgemeinen Formeln D erivate des ι, 2, 4-triazine of the general formulas
R-C6 3C-S-RC 6 3 CS-
Ν —ΝΝ —Ν
undand
CO-NCO-N
R-CR-C
,C-S-X1 , CSX 1
N-NN-N
worin R einen gegebenenfalls substituierten heterocyclischen Rest, X3 Wasserstoff oder einen Alkyl-, Aral- -' kyi-; Aryl- oder heterocyclischen Rest und X2 und X3 Wasserstoff;· Alkyl-, Aralkyl-, Aryl- öder heterocyclische Reste bedeuten, sind bisher nicht bekanntgeworden. Wie gefunden wurde, können sie als Zwischenprodukte oder zur Herstellung von Arzneimitteln dienen.wherein R is an optionally substituted heterocyclic radical, X 3 is hydrogen or an alkyl, aral - 'kyi-; Aryl or heterocyclic radicals and X 2 and X 3 are hydrogen; · alkyl, aralkyl, aryl or heterocyclic radicals are not known to date. As has been found, they can serve as intermediates or for the manufacture of pharmaceuticals.
Man kann die neuen Verbindungen synthetisieren, 25 indem man Thiosemicarbazone von cc-Ketosäuren der allgemeinen FormernThe new compounds can be synthesized, 25 by taking thiosemicarbazones of cc-keto acids of the general formulas
COOH HN-X2 COOH HN-X 2
N-NN-N
COOH HNCOOH HN
C-S-X1 CSX 1
R-CR-C
C-S-X1 CSX 1
X.«X. «
worin R, X1, X2 und X3 die oben gegebene Bedeutung haben bzw. deren reaktionsfähige funktionelle Derivate mit ringschließenden Mitteln und hierauf gegebenenfalls zur nachträglichen Einführung der Reste X1 und X3 noch mit Alkylierungs- oder Aralkylierungsmitteln behandelt.wherein R, X 1 , X 2 and X 3 have the meaning given above or their reactive functional derivatives are treated with ring-closing agents and then optionally with alkylating or aralkylating agents for the subsequent introduction of the radicals X 1 and X 3.
Als ringschließende Mittel kommen z. B. Alkalien, wie Lösungen von Natriumcarbonat, Kaliumcarbonat oder Natriumhydroxyd, in Betracht; in der Mercaptogruppe substituierte Verbindungen gehen beim Erhitzen in Alkohol ohne weitere Zusätze in die ge- -. wünschten Triazinderivate über.As a ring-closing agent, for. B. alkalis, such as solutions of sodium carbonate, potassium carbonate or sodium hydroxide, into consideration; Compounds substituted in the mercapto group go when heated in alcohol without further additives in the -. wanted triazine derivatives over.
Als Alkylierungs- und Äralkylierüngsmittel eignen sich reaktionsfähige Ester von aliphatischen und araliphatischen Alkoholen in Gegenwart von Alkalien. Beispielsweise seien Methyljodid, Dimethylsulfat, To-. luolsulfonsäuremethylester, Äthylbromid, Diäthylsulfat, äthylschwefelsaures Natrium, Propylchlorid, Isopropylbromid, Allylbromid und Benzylchlorid genannt. Die genannten Mittel reagieren zuerst mit der Mercaptogruppe, sofern diese frei ist; in zweiter Linie wird das Wasserstoffatom in Stellung 2 substituiert. Suitable as alkylating and aralkylating agents reactive esters of aliphatic and araliphatic alcohols in the presence of alkalis. Examples include methyl iodide, dimethyl sulfate, To-. luenesulfonic acid methyl ester, ethyl bromide, diethyl sulfate, Sodium ethylsulphurate, propyl chloride, isopropyl bromide, allyl bromide and benzyl chloride are called. The agents mentioned react first with the mercapto group, provided that it is free; in second Line the hydrogen atom in position 2 is substituted.
Die als Ausgangsprodukte benötigten Thiosemicarbazone von α-Ketosäuren bzw. von deren reaktionsfähigen funktioneilen Derivaten lassen sich z.B. in üblicher Weise aus den a-Ketosäuren oder deren funktionellen Derivaten und Thiosemicarbazid bzw. entsprechend substituierten Thiosemicarbaziden her- _ stellen. An Stelle von α-Ketosäuren können auch„ die in manchen Fällen zugänglichen a-Thioketosäuren verwendet werden. Ferner kann man in Stellung 4 substituierte Thiosemicarbazone z. B. auch herstellen, indem man die α-Ketosäuren oder deren reaktionsfähige funktionelle Derivate zunächst in die Hydrazone überführt und diese mit Isothiocyanaten, insbesondere Alkylsenfölen, umsetzt.The thiosemicarbazones required as starting materials of α-keto acids or of their reactive ones functional derivatives can be prepared, for example, in the usual way from the a-keto acids or their functional Derivatives and thiosemicarbazide or correspondingly substituted thiosemicarbazides place. Instead of α-keto acids, “the in some cases accessible a-thioketo acids can be used. It is also possible to substitute in the 4 position Thiosemicarbazones e.g. B. also produce by the α-keto acids or their reactive functional derivatives first transferred into the hydrazones and these with isothiocyanates, in particular Alkyl mustard oils.
Als α-Ketosäuren bzw. a-Thioketosäuren, welche zur Umsetzung mit Thiosemicarbaziden in Frage kommen, seien beispielsweise genannt: Furyl-(2)- und Furyl-(3)-glyoxylsäure, 5-Methylfuryl- (2) -glyoxylsäure, 5-Nitrofuryl-(2)-glyoxylsäure, Furyl-(2)- und Furyl-(3)-brenztraubensäure,j5-Furyl-(2)-a-sulfhydrylacrylsäure (Furyl-(2)-thiobrenztraubensäure), Thienyl-(2)- und Thienyl-(3)-glyoxylsäure, 5-Chlorthienyl-(2)-glyoxylsäure, Thienyl-(2)-brenztraubensäure, Pyrryl-(2)- und Pyrryl-(3)-glyoxylsäure, N-Methylpyrryl-(2)-glyoxylsäure, Imidazolyl-(4)-glyoxylsäure, Thiazolyl - (4) - glyoxylsäure, 2-Aminothiazolyl-(4) - glyoxylsäure, 1, 2, 4-Oxadiazolyl-(5)-brenztraubensäure, Benzofuryl-(2)- und -(3)-glyoxylsäure, Thionaphthenyl-(2)- und -(3)-glyoxylsäure, Indolyl-(3)-glyoxylsäure, Indolyl - (3) -brenztraubensäure, β - Indolyl - (3) - α - sulfhydrylacrylsäure (Indolyl-(3)-thiobrenztraubensäure), Pyridyl-(2)-, Pyridyl-(3)- und Pyridyl-(4)-glyoxylsäure, Pyridyl-(2)-,Pyridyl-(3)-undPyridyl-(4)-brenztraubensäure, Chinolyl-(2)-glyoxylsäure, Chinolyl-(2)-brenztraubensäure, Chinolyl-(4)-brenztraubensäure.Examples of α-keto acids or a-thioketo acids which can be used for reaction with thiosemicarbazides are: furyl (2) and furyl (3) glyoxylic acid, 5-methylfuryl (2) glyoxylic acid, 5- Nitrofuryl- (2) -glyoxylic acid, furyl- (2) - and furyl- (3) -pyruvic acid, j5-furyl- (2) -a-sulfhydrylacrylic acid (furyl- (2) -thio-pyruvic acid), thienyl- (2) - and thienyl (3) glyoxylic acid, 5-chlorothienyl (2) glyoxylic acid, thienyl (2) pyruvic acid, pyrryl (2) and pyrryl (3) glyoxylic acid, N-methylpyrryl (2) - glyoxylic acid, imidazolyl- (4) -glyoxylic acid, thiazolyl- (4) -glyoxylic acid, 2-aminothiazolyl- (4) -glyoxylic acid, 1, 2, 4-oxadiazolyl- (5) -pyruvic acid, benzofuryl- (2) - and - (3) glyoxylic acid, thionaphthenyl (2) and (3) glyoxylic acid, indolyl (3) glyoxylic acid, indolyl (3) pyruvic acid, β - indolyl - (3) - α - sulfhydrylacrylic acid (indolyl) (3) -thio-pyruvic acid), pyridyl- (2) -, pyridyl- (3) - and pyridyl- (4) -glyoxylic acid, pyridyl- (2) -, pyridyl- (3) -and pyridyl- (4) -pyridyl ubenic acid, quinolyl- (2) -glyoxylic acid, quinolyl- (2) -pyruvic acid, quinolyl- (4) -pyruvic acid.
Als substituierte Thiosemicarbazide seien genannt: 2-Methyl-, 2-Äthyl-, 2-Allyl-, 2-Butyl-, 2-Benzyl-, 2-Phenylthiosemicarbazid; S-Methyl-, S-Propyl-, S-Benzylthiosemicarbazid; 4-Methyl-, 4-Äthyl-, 4-Isol-y 4-Allyl-, 4-Isoamyl-, 4-Benzyl, 4-Phenäthyl-, 4-Phenyl-, 4-p-Tolyl-, 4-p-Anisyl-, 4-Pyridyl-(jÖ)-methyl-, 4-Furfurylthiosemicarbazid; 2-Methyl-S-methyl-, 2-Äthyl -S-benzylthiosemicarbazid; 4-Methyl-S-phenyl-, 4-Äthyl-S-äthylthiosemicarbazid; S-Acetylthiosemicarbazid, S-Benzoylthiosemicarbazid.Substituted thiosemicarbazides that may be mentioned are: 2-methyl-, 2-ethyl-, 2-allyl-, 2-butyl-, 2-benzyl-, 2-phenylthiosemicarbazide; S-methyl, S-propyl, S-benzylthiosemicarbazide; 4-methyl-, 4-ethyl-, 4-isol-y 4-allyl, 4-isoamyl, 4-benzyl, 4-phenethyl, 4-phenyl-, 4-p-tolyl-, 4-p-anisyl-, 4-pyridyl- (jÖ) -methyl-, 4-furfurylthiosemicarbazide; 2-methyl-S-methyl-, 2-ethyl -S-benzylthiosemicarbazide; 4-methyl-S-phenyl-, 4-ethyl-S-ethylthiosemicarbazide; S-acetylthiosemicarbazide, S-benzoyl thiosemicarbazide.
Die aufgeführten α-Ketosäuren und Thiosemicarbazide sind zum Teil bekannt; soweit dies nicht der Fall ist, können sie nach Methoden hergestellt werden, die für die Herstellung der bekannten Verbindungen in der Literatur beschrieben wurden.Some of the listed α-keto acids and thiosemicarbazides are known; if this is not the case is, they can be prepared by methods used for the preparation of the known compounds in have been described in the literature.
Die nachfolgenden Beispiele sollen zur näheren Erläuterung der Erfindung dienen; Teile bedeuten darin stets Gewichtsteile, die Temperaturangaben beziehen sich auf Centigrade.The following examples are intended to explain the invention in more detail; Parts mean in it always parts by weight, the temperature data relate to centigrade.
23 Teile Thienyl-(2)-glyoxylsäurethiosemicarbazon vom Schmp. 1820, hergestellt z. B. aus Thienyl-(2)-glyoxylsäure und Thiosemicarbazid, werden in 250 Teilen Wasser bis zur phenolphthaleinalkalischen Reaktion mit verdünnter Natronlauge versetzt und die Lösung 3 Stunden am Rückfluß gekocht. Nach dem Abkühlen wird mit Salzsäure kongosauer gestellt und der Niederschlag abfiltriert. Nach Umkristallisieren aus Dioxan und Wasser erhält man 6-Thienyl-3-mercapto-i, 2, 4-triazin-5(2H)-on, das bei 2830 unter Zersetzung schmilzt.23 parts of thienyl- (2) -glyoxylsäurethiosemicarbazon of melting point 182 0 , manufactured e.g. B. from thienyl (2) glyoxylic acid and thiosemicarbazide, dilute sodium hydroxide solution is added to 250 parts of water until the phenolphthalein-alkaline reaction is achieved, and the solution is refluxed for 3 hours. After cooling, it is acidified to Congo with hydrochloric acid and the precipitate is filtered off. After recrystallization from dioxane and water, 6-thienyl-3-mercapto-i, 2, 4-triazin-5 (2H) -one, which melts at 283 ° with decomposition, is obtained.
28 Teile Thienyl-(2)-glyoxylsäureäthylester-4'-äthylthiosemicarbazon vom Schmp. I2O°> hergestellt z. B. aus Thienyl-(2)-glyoxylsäureäthylester und 4-Äthylthiosemicarbazid, werden in 400 Teilen Wasser bis zur phenolphthaleinalkalischen Reaktion mit Natronlauge versetzt und 48 Stunden bei Zimmertemperatur stehengelassen. Dann wird mit Essigsäure angesäuert und der Niederschlag abgesaugt. Das so erhaltene 6-Thienyl-4-äthyl-3-mercapto-i,2,4-triazin-5 (4H)-on schmilzt nach Umkristallisieren aus Alkohol bei 253° unter Zersetzung.28 parts of ethyl thienyl (2) glyoxylate 4'-ethylthiosemicarbazone from melting point I2O °> produced z. B. from thienyl (2) glyoxylic acid ethyl ester and 4-ethylthiosemicarbazide, are in 400 parts of water to a phenolphthalein-alkaline reaction with sodium hydroxide solution added and left to stand for 48 hours at room temperature. Then it is acidified with acetic acid and the precipitate sucked off. The 6-thienyl-4-ethyl-3-mercapto-i, 2,4-triazin-5 (4H) -one thus obtained After recrystallization from alcohol, it melts at 253 ° with decomposition.
In analoger Weise erhält man aus Thienyl-(2)-glyoxylsäureäthylester - 4'- allylthiosemicarbazon vom Schmp. ioi° das ö-Thienyl^-allyl-s-mercapto-i, 2,4- m triazin-5(4H)-on vom Schmp. 2240.In an analogous manner, from thienyl- (2) -glyoxylic acid ethyl ester-4'-allylthiosemicarbazone of mp from m.p. 224 0 .
Ferner wurden in entsprechender Weise hergestellt:In addition, the following were produced in a corresponding manner:
6-(a-Thienyl)-3-methylmercapto-i, 2, 4-triazin-5 (2H)-on, F. = 2580 unter Zersetzung;6- (a-Thienyl) -3-methylmercapto-i, 2, 4-triazin-5 (2H) -one, m.p. = 258 0 with decomposition;
6-(a-Thienyl)-2-benzyl-3-mercapto-i, 2,4-triazin- ii; 5 (2H)-on, F. = 2520 unter Zersetzung;6- (a-thienyl) -2-benzyl-3-mercapto-i, 2,4-triazine-ii ; 5 (2H) -one, m.p. = 252 0 with decomposition;
6-(a-Pyrryl)-3-mercapto-i, 2, 4-triazin-5(2H)-on, F. = 2900 unter Zersetzung;6- (a-pyrryl) -3-mercapto-i, 2, 4-triazin-5 (2H) -one, m.p. = 290 0 with decomposition;
6-(a-Pyridyl)-3-mercapto-i, 2,4-triazin-5(2H)-on, F. = 324° unter Zersetzung;6- (a-Pyridyl) -3-mercapto-i, 2,4-triazin-5 (2H) -one, M.p. = 324 ° with decomposition;
6-(/J-Pyridyl)-3-mercapto-i, 2,4-triazin-5(2H)-on, F. = 3360 unter Zersetzung;6 - (/ J-pyridyl) -3-mercapto-i, 2,4-triazin-5 (2H) -one, m.p. = 336 0 with decomposition;
ö-Chinaldyl-s-mercapto-i, 2, 4-triazin-5(2H)-on, F. = 2900 unter Zersetzung;δ-quinaldyl-s-mercapto-i, 2, 4-triazin-5 (2H) -one, m.p. = 290 0 with decomposition;
6-[8'-Oxychinolyl-(5')]-3-mercapto-i, 2, 4-triazin- ia> 5(2H)-on, F. = über 3000 unter Zersetzung.6- [8'-Oxyquinolyl- (5 ')] -3-mercapto-i, 2, 4-triazin- ia> 5 (2H) -one, F. = over 300 0 with decomposition.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH705609X | 1950-08-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE860949C true DE860949C (en) | 1952-12-29 |
Family
ID=4530356
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEG6671A Expired DE860949C (en) | 1950-08-01 | 1951-08-01 | Process for the preparation of new derivatives of 1, 2, 4-triazine |
Country Status (3)
| Country | Link |
|---|---|
| DE (1) | DE860949C (en) |
| FR (1) | FR1040217A (en) |
| GB (1) | GB705609A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3139431A (en) * | 1960-02-23 | 1964-06-30 | Norwich Pharma Co | 6-(5-nitro-2-furyl) azauracil |
| DE1670912A1 (en) * | 1967-08-18 | 1971-03-18 | Bayer Ag | 1,2,4-triazin-5-ones |
-
1951
- 1951-07-31 FR FR1040217D patent/FR1040217A/en not_active Expired
- 1951-07-31 GB GB18061/51A patent/GB705609A/en not_active Expired
- 1951-08-01 DE DEG6671A patent/DE860949C/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3139431A (en) * | 1960-02-23 | 1964-06-30 | Norwich Pharma Co | 6-(5-nitro-2-furyl) azauracil |
| DE1670912A1 (en) * | 1967-08-18 | 1971-03-18 | Bayer Ag | 1,2,4-triazin-5-ones |
Also Published As
| Publication number | Publication date |
|---|---|
| FR1040217A (en) | 1953-10-13 |
| GB705609A (en) | 1954-03-17 |
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