CH605843A5 - Prepn. of (3)-hydroxy-(1,2,4)-triazole derivs. - Google Patents
Prepn. of (3)-hydroxy-(1,2,4)-triazole derivs.Info
- Publication number
- CH605843A5 CH605843A5 CH815276A CH815276A CH605843A5 CH 605843 A5 CH605843 A5 CH 605843A5 CH 815276 A CH815276 A CH 815276A CH 815276 A CH815276 A CH 815276A CH 605843 A5 CH605843 A5 CH 605843A5
- Authority
- CH
- Switzerland
- Prior art keywords
- formula
- compound
- reaction
- hydroxy
- carbon atoms
- Prior art date
Links
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- LZTSCEYDCZBRCJ-UHFFFAOYSA-N 1,2-dihydro-1,2,4-triazol-3-one Chemical class OC=1N=CNN=1 LZTSCEYDCZBRCJ-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 claims description 3
- 239000012442 inert solvent Substances 0.000 claims description 3
- 238000002955 isolation Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000007363 ring formation reaction Methods 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- 125000002252 acyl group Chemical group 0.000 claims 1
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 150000001340 alkali metals Chemical class 0.000 claims 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims 1
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical class OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 6
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- -1 alkyl chloroformate Chemical compound 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- QPJDMGCKMHUXFD-UHFFFAOYSA-N cyanogen chloride Chemical compound ClC#N QPJDMGCKMHUXFD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- WRJOIKFTCSTNRQ-UHFFFAOYSA-N 3-methoxy-2-propan-2-yl-1h-1,2,4-triazol-5-one Chemical compound COC1=NC(O)=NN1C(C)C WRJOIKFTCSTNRQ-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 125000005910 alkyl carbonate group Chemical group 0.000 description 1
- VRPHXQGTAUWCFZ-UHFFFAOYSA-N amino(propan-2-yl)cyanamide Chemical compound CC(C)N(N)C#N VRPHXQGTAUWCFZ-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- ZKLHMTOTLCILPA-UHFFFAOYSA-N methyl n-amino-n-propan-2-ylcarbamimidate Chemical compound COC(=N)N(N)C(C)C ZKLHMTOTLCILPA-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005645 nematicide Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-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
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles 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
- C07D249/12—Oxygen or sulfur atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
Prepn. of (3)-hydroxy-(1,2,4)-triazole derivs. by reacting (1)-cyano hydrazines with (thio)alcohols and cyclising
Description
Die vorliegende Erfindung betrifft ein Verfahren zur Her stellung von 3-Hydroxy-1,2,4-tnazolderivaten der Formel I
EMI1.1
in welcher
R1 und R2 je eine geradkettige oder verzweigte Alkylgruppe mit 1 bis 6 Kohlenstoffatomen oder eine Cycloalkylgruppe mit 3 bis 6 Kohlenstoffatomen bedeuten.
Die 3-Hydroxy-1,2,4-triazolderivate der Formel I sind wertvolle Zwischenprodukte zur Herstellung von Phosphorsäureestern, die als Schädlingsbekämpfungsmittel, insbesondere als Insektizide und Nematizide, verwendet werden können.
Derartige Phosphorsäureester und ihre Verwendung sind in der US-Patentschrift 3.867.398 beschrieben. Es ist bekannt, 3-Hydroxy-1,2,4triazolderivate der Formel I durch Umsetzung von entsprechenden l-Alkyl-3-hydroxy-5-chlor-1,2,4-triazolen mit Alkylmercaptiden bzw. Alkoholaten herzustellen (vgl. US-Patentschrift 3.867.398). Die l-Alkyl-3-hydroxy-5 chlor-1,2,4triazole werden ihrerseits erhalten, indem man ein l-Alkylsemicarbazid mit Ameisensäure zum entsprechenden l-Alkyl-3-hydroxy-1,2,4-triazol umsetzt (bei. dtsch. Chem.
Ges. 26, 2613, (1893)) und dieses anschliessend in 5-Stellung chloriert (vgl. US-Patentschrift 3.867.396). Dieses bekannte Verfahren benötigt nicht nur eine grosse Zahl von Reaktionsstufen, sondern es vermag auch im Hinblick auf die erzielbaren Ausbeuten nicht zu befriedigen.
Es wurde nun gefunden, dass man die 3-Hydroxy-1,2,4- triazolderivate der Formel I in einfacher Weise herstellen kann, wenn man an ein l-Alkyl-bzu. l-Cycloalkyl-1-cyanohydrazin der Formel II
EMI1.2
in welcher Ri die unter Formel I angegebene Bedeutung hat, eine Verbindung der Formel III
EMI1.3
in welcher Ri die unter Formel I angegebene Bedeutung hat, anlagert und das Additionsprodukt anschliessend durch Umsetzung mit einer Verbindung der Formel IV
EMI1.4
in welcher R3 und R4 unabhängig voneinander Chlor oder eine Alkoxygruppe mit 1 bis 4 Kohlenstoffatomen bedeutet, cyclisiert.
Das erfindungsgemässe Verfahren wird vorteilhaft in einem inerten Lösungsmittel durchgeführt. Als inerte Lösungsmittel kommen insbesondere chlorierte Kohlenwasserstoffe wie Methylenchlorid, Chloroform, Kohlenstofftetrachlorid, und Tetrachloräthan, Aether, wie niedere Dialkyläther, Tetrahydrofuradgod: Dioxan, oder vom Rest R2 abgeleitete Alkohole in Betracht.
Die Umsetzung einer Verbindung der Formel II mit einer Verbindung der Formel m wird vorzugsweise in Gegenwart von Basen, z.B. Alkalimetallhydroxid, wie Natrium-und Kaliumhydroxid, oder Alkoholaten, wie Natrium- und Saliulnalkoholaten, durchgeführt
Das erfirsdungsgemässe Verfahren wird vorzugsweise in der Weise durchgeführt,
dass man entweder eine Lösung einer Verbindung der Formel m mit einer der vorgenannte Basen vorlegt und die Verbindung der Formel II bei Temperaturen zwischen 0 und 250"C, vorzugsweise 15 bis 1200C, in diese Lösung eintropft oder die Verbindung der Formel II vorlegt und eine Lösung einer Verbindung der Formel m mit einer der vorgenannten Basen bei Temperaturen zwischen 0 und 250"C vorzugsweise 15 bis 1200C, zugibt.
Die hierbei gebildeten O-R2-isosemicarbazide der Formel V
EMI1.5
in welcher R1 und R2 die unter Formel I angegebene Bedeutung haben, werden vorteilhaft ohne Isolierung unmittelbar anschliessend durch Umsetzung mit Phosgen oder einem Chlorameisensäureniederalkylester oder einem Kohlen säureniederalkylester cyclisiert. Die Cyclisierung wird vorzugsweise bei Temperaturen zwischen 20 und 100"C durchgeführt, wobei die Reaktionspartner zunächst bei niederen Temperaturen von etwa 20 bis 50"C vereinigt werden und die Reaktion durch nachfolgendes Erhitzen zu Ende gebracht wird.
Es ist vorteilhaft, die Cyclisierung in Gegenwart einer Base durchzuführen, wobei als Basen z.B. Pyndin, Triäthylamin, Alkalimetallhydroxide, -carbonate und -bicarbonate in Betracht kommen.
Die 3-Hydroxy-l,2,4triazolderivate der Formel I können aus wässrigen Reaktionsgemischen nach Ansäuern entweder durch Kristallisation oder durch Extraktion isoliert werden.
Aus Reaktionsgemischen, die eines der vorgenannten organischen Lösungsmittel enthalten, können die Endprodukte entweder durch Zugabe von Eisessig ausgefällt oder nach Abdampfen des Lösungsmittels durch Kristallisation oder Extraktion des Rückstandes gewonnen werden. Sowohl für die Extraktion aus wässrigen Reaktionsmischungen als auch für die Extraktion des nach dem Abdampfen des Alkohols erhaltenen Rückstandes sind insbesondere chlorierte Kohlenwasserstoffe, wie Methylenchlorid, Chloroform, Kohlenstofftetrachlorid und Tetrachloräthan als Lösungsmittel geeignet.
Die als Ausgangsmaterial verwendeten Verbindungen der Formel II können durch Umsetzung eines entsprechenden Alkyl-oder Cycloalkylhydrazins mit Chlorcyan in Gegenwart eines säurebindenden Mittels erhalten werden. Die Umsetzung wird vorteilhaft in einem zweiphasigen Reaktionsmedium bestehend aus Wasser und einem mit Wasser nicht mischbaren organischen Lösungsmittel durchgeführt, wobei als Lösungsmittel insbesondere niedere, halogenierte Kohlenwasserstoffe, insbesondere Methylenchlorid, in Betracht kommen. Die Umsetzung wird vorteilhaft bei Temperaturen zwischen 0 C und 30"C vorgenommen.
Als säurebindende Mittel eignen sich insbesondere Alkalimetallhydroxide, -carbonate und insbesondere -hydrogencarbonate. Die Umsetzung wird beispielsweise so durchgeführt, dass man einer Lösung eines entsprechenden Hydrazins in Methylenchlorid eine wässrige Lösung des säurebindenden Mittels zufügt und unter heftigem Rühren Chlorcyan eintropft bzw. einleitet. Nach beendigter Umsetzung kann das gebildete l-Alkyl-bzw. l-Cycloalkyl-l-cyanohydrazin durch Abtrennung der wässrigen Phase und Abdampfen des organischen Lösungsmittels im Vakuum isoliert werden.
Durch das erfindungsgemässe Verfahren wird es möglich, die 3-Hydroxy-1,2,4-triazolderivate der Formel I in besonders einfacher Weise in sehr guten Ausbeuten herzustellen.
Das erfindungsgemässe Verfahren wird durch das nachfolgende Beispiel näher erläutert:
Beispiel
Zu einer Lösung von 0,5 g Natrium-Metall in 32,1 g (1,0 Mol) Methanol tropft man anfänglich bei Siedetemperatur 99,0 g (1,0 Mol) l-Isopropyl-l-cyanohydrazin ein, wobei eine exotherme Reaktion stattfindet und ein Temperaturanstieg des Reaktionsgemisches gegen Ende der Reaktion bis auf l100C eintritt. Beim Erkalten kristallisiert die Reaktionsmischung. Das so erhaltene O-Methyl-2-isopropyl-isosemicarbazid wird ohne weitere Isolierung in einer Mischung von 202 g (2,0 Mol) Triäthylamin und 500 ml Aether gelöst.
Diese Lösung tropft man bei 0 C zu einer vorgelegten Lösung von 99,0 g (1,0 Mol) Phosgen in 500 ml Aether zu.
Anschliessend kocht man das Reaktionsgemisch noch 1 Stunde am Rückfluss und filtriert das entstandene Triäthylamin Hydrochlorid ab. Nach dem Abdampfen des Aethers kristallisiert der ölige Rückstand bei Kühlen im Eisbad durch.
Durch Umkristallisation aus Aether wird das i4sopropyl-3- hydroxy-5-methoxy-1,2,4-triazol vom Schmelzpunkt 104-105 C erhalten.
The present invention relates to a process for the preparation of 3-hydroxy-1,2,4-tnazole derivatives of the formula I
EMI1.1
in which
R1 and R2 each represent a straight-chain or branched alkyl group with 1 to 6 carbon atoms or a cycloalkyl group with 3 to 6 carbon atoms.
The 3-hydroxy-1,2,4-triazole derivatives of the formula I are valuable intermediates for the preparation of phosphoric acid esters which can be used as pesticides, in particular as insecticides and nematicides.
Such phosphoric acid esters and their use are described in US Pat. No. 3,867,398. It is known that 3-hydroxy-1,2,4-triazole derivatives of the formula I can be prepared by reacting corresponding 1-alkyl-3-hydroxy-5-chloro-1,2,4-triazoles with alkyl mercaptides or alcoholates (see US Pat. Patent 3,867,398). The 1-alkyl-3-hydroxy-5-chloro-1,2,4-triazoles are in turn obtained by reacting an 1-alkyl semicarbazide with formic acid to give the corresponding 1-alkyl-3-hydroxy-1,2,4-triazole (see. German Chem.
Ges. 26, 2613, (1893)) and this is then chlorinated in the 5-position (see US Pat. No. 3,867,396). This known process not only requires a large number of reaction stages, but it is also unsatisfactory in terms of the yields that can be achieved.
It has now been found that the 3-hydroxy-1,2,4-triazole derivatives of the formula I can be prepared in a simple manner if one connects to an l-alkyl-bzu. l-Cycloalkyl-1-cyanohydrazine of the formula II
EMI1.2
in which Ri has the meaning given under formula I, a compound of formula III
EMI1.3
in which Ri has the meaning given under formula I, and the addition product is then added by reaction with a compound of formula IV
EMI1.4
in which R3 and R4 are independently chlorine or an alkoxy group having 1 to 4 carbon atoms, cyclizes.
The process according to the invention is advantageously carried out in an inert solvent. Particularly suitable inert solvents are chlorinated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride and tetrachloroethane, ethers such as lower dialkyl ethers, tetrahydrofuran: dioxane, or alcohols derived from the radical R2.
The reaction of a compound of formula II with a compound of formula m is preferably carried out in the presence of bases, e.g. Alkali metal hydroxide, such as sodium and potassium hydroxide, or alcoholates, such as sodium and saline alcoholates
The method according to the invention is preferably carried out in such a way
that either a solution of a compound of the formula m with one of the abovementioned bases is introduced and the compound of the formula II is dripped into this solution at temperatures between 0 and 250 ° C., preferably 15 to 1200 ° C., or the compound of the formula II is introduced and a solution a compound of the formula m with one of the abovementioned bases at temperatures between 0 and 250 ° C., preferably 15 to 1200 ° C., is added.
The O-R2-isosemicarbazides of the formula V formed here
EMI1.5
in which R1 and R2 have the meaning given under formula I, are advantageously cyclized immediately thereafter, without isolation, by reaction with phosgene or a lower alkyl chloroformate or a lower alkyl carbonate. The cyclization is preferably carried out at temperatures between 20 and 100 "C., the reactants first being combined at low temperatures of about 20 to 50" C. and the reaction being brought to an end by subsequent heating.
It is advantageous to carry out the cyclization in the presence of a base, e.g. Pyndine, triethylamine, alkali metal hydroxides, carbonates and bicarbonates come into consideration.
The 3-hydroxy-1,2,4-triazole derivatives of the formula I can be isolated from aqueous reaction mixtures after acidification either by crystallization or by extraction.
From reaction mixtures containing one of the aforementioned organic solvents, the end products can either be precipitated by adding glacial acetic acid or, after the solvent has been evaporated off, obtained by crystallization or extraction of the residue. Chlorinated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride and tetrachloroethane, are particularly suitable solvents both for the extraction from aqueous reaction mixtures and for the extraction of the residue obtained after the alcohol has been evaporated off.
The compounds of the formula II used as starting material can be obtained by reacting a corresponding alkyl or cycloalkyl hydrazine with cyanogen chloride in the presence of an acid-binding agent. The reaction is advantageously carried out in a two-phase reaction medium consisting of water and a water-immiscible organic solvent, in particular lower, halogenated hydrocarbons, in particular methylene chloride, being suitable solvents. The reaction is advantageously carried out at temperatures between 0.degree. C. and 30.degree.
Particularly suitable acid-binding agents are alkali metal hydroxides, carbonates and, in particular, hydrogen carbonates. The reaction is carried out, for example, by adding an aqueous solution of the acid-binding agent to a solution of a corresponding hydrazine in methylene chloride and adding or introducing cyanogen chloride in drops with vigorous stirring. After the reaction has ended, the l-alkyl or. l-Cycloalkyl-l-cyanohydrazine can be isolated by separating off the aqueous phase and evaporating the organic solvent in vacuo.
The process according to the invention makes it possible to prepare the 3-hydroxy-1,2,4-triazole derivatives of the formula I in a particularly simple manner in very good yields.
The method according to the invention is explained in more detail by the following example:
example
To a solution of 0.5 g of sodium metal in 32.1 g (1.0 mol) of methanol, 99.0 g (1.0 mol) of 1-isopropyl-1-cyanohydrazine are initially added dropwise at the boiling point, an exothermic reaction Reaction takes place and the temperature of the reaction mixture rises towards the end of the reaction up to 110C. The reaction mixture crystallizes on cooling. The O-methyl-2-isopropyl-isosemicarbazide thus obtained is dissolved without further isolation in a mixture of 202 g (2.0 mol) of triethylamine and 500 ml of ether.
This solution is added dropwise at 0 C to a solution of 99.0 g (1.0 mol) of phosgene in 500 ml of ether.
The reaction mixture is then refluxed for a further hour and the triethylamine hydrochloride formed is filtered off. After the ether has evaporated, the oily residue crystallizes through when cooled in an ice bath.
Isopropyl-3-hydroxy-5-methoxy-1,2,4-triazole with a melting point of 104-105 ° C. is obtained by recrystallization from ether.
Claims (1)
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH815276A CH605843A5 (en) | 1976-06-25 | 1976-06-25 | Prepn. of (3)-hydroxy-(1,2,4)-triazole derivs. |
| US05/707,148 US4055572A (en) | 1975-08-06 | 1976-07-20 | Process for the production of 3-hydroxy-1,2,4-triazole derivatives |
| DE19762634854 DE2634854A1 (en) | 1975-08-06 | 1976-08-03 | PROCESS FOR THE PREPARATION OF 3-HYDROXY-1,2,4-TRIAZOLE DERIVATIVES |
| IL50199A IL50199A (en) | 1975-08-06 | 1976-08-04 | Production of 3-hydroxy-1,2,4-triazole derivatives |
| CA258,385A CA1063612A (en) | 1975-08-06 | 1976-08-04 | Process for the production of 3-hydroxy-1,2,4-triazole derivatives |
| FR7623927A FR2320296A1 (en) | 1975-08-06 | 1976-08-05 | PROCESS FOR PREPARATION OF 3-HYDROXY-1,2,4-TRIAZOLE DERIVATIVES |
| GB32706/76A GB1552982A (en) | 1975-08-06 | 1976-08-05 | Process for the production of 3-hydroxy 1,2,4-triazole derivatives |
| JP51093891A JPS6036428B2 (en) | 1975-08-06 | 1976-08-06 | Method for producing 3-hydroxy-1,2,4-triazole derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH815276A CH605843A5 (en) | 1976-06-25 | 1976-06-25 | Prepn. of (3)-hydroxy-(1,2,4)-triazole derivs. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH605843A5 true CH605843A5 (en) | 1978-10-13 |
Family
ID=4335963
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH815276A CH605843A5 (en) | 1975-08-06 | 1976-06-25 | Prepn. of (3)-hydroxy-(1,2,4)-triazole derivs. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH605843A5 (en) |
-
1976
- 1976-06-25 CH CH815276A patent/CH605843A5/en not_active IP Right Cessation
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| Date | Code | Title | Description |
|---|---|---|---|
| PL | Patent ceased | ||
| PL | Patent ceased |