DE2109454A1 - Fungicidal n-(2-acylaminophenyl)-n,n-bis(alkoxycarbonyl)-guanidines - from 2-acrylaminoanilines and s-alkyl n,n-bis(alkoxycarbonyl) isothiazole - Google Patents
Fungicidal n-(2-acylaminophenyl)-n,n-bis(alkoxycarbonyl)-guanidines - from 2-acrylaminoanilines and s-alkyl n,n-bis(alkoxycarbonyl) isothiazoleInfo
- Publication number
- DE2109454A1 DE2109454A1 DE19712109454 DE2109454A DE2109454A1 DE 2109454 A1 DE2109454 A1 DE 2109454A1 DE 19712109454 DE19712109454 DE 19712109454 DE 2109454 A DE2109454 A DE 2109454A DE 2109454 A1 DE2109454 A1 DE 2109454A1
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- Germany
- Prior art keywords
- alkyl
- carbon atoms
- halogen
- alkoxy
- stands
- 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
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- 125000004453 alkoxycarbonyl group Chemical group 0.000 title claims abstract 5
- 230000000855 fungicidal effect Effects 0.000 title abstract 2
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 title 1
- VBCYIWDVPBUMAD-UHFFFAOYSA-N n-(2-aminophenyl)prop-2-enamide Chemical class NC1=CC=CC=C1NC(=O)C=C VBCYIWDVPBUMAD-UHFFFAOYSA-N 0.000 title 1
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 34
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 23
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 21
- 150000002367 halogens Chemical class 0.000 claims abstract description 15
- QRJZGVVKGFIGLI-UHFFFAOYSA-N 2-phenylguanidine Chemical compound NC(=N)NC1=CC=CC=C1 QRJZGVVKGFIGLI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 125000002252 acyl group Chemical group 0.000 claims abstract description 3
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims abstract description 3
- 125000004663 dialkyl amino group Chemical group 0.000 claims abstract description 3
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 3
- 150000007524 organic acids Chemical class 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- 125000005843 halogen group Chemical group 0.000 claims abstract 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 42
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical class NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 239000003085 diluting agent Substances 0.000 abstract description 3
- 125000004391 aryl sulfonyl group Chemical group 0.000 abstract description 2
- 239000003377 acid catalyst Substances 0.000 abstract 1
- -1 alkyl radical Chemical class 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000417 fungicide Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- QRKJNCRCYBKANP-UHFFFAOYSA-N 2-amino-n-phenylacetamide Chemical compound NCC(=O)NC1=CC=CC=C1 QRKJNCRCYBKANP-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
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 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
- 239000006227 byproduct Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- HRDXJKGNWSUIBT-UHFFFAOYSA-N methoxybenzene Chemical group [CH2]OC1=CC=CC=C1 HRDXJKGNWSUIBT-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- MPXAYYWSDIKNTP-UHFFFAOYSA-N n-(2-aminophenyl)acetamide Chemical compound CC(=O)NC1=CC=CC=C1N MPXAYYWSDIKNTP-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 150000004987 o-phenylenediamines Chemical class 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical class NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Verfahren zur Herstellung von Phenylguanidin-Derivaten Die vorliegende Erfindung betrifft ein chemisch eigenartiges Verfahren zur Herstellung von Phenylguanidin-Derivaten, welche als Fungizide verwendet werden können.Process for the preparation of phenylguanidine derivatives The present The invention relates to a chemically peculiar process for the production of phenylguanidine derivatives, which can be used as fungicides.
Es ist Gegenstand eines älteren Rechts, daß man.fungizid wirksame Phenylguanidin-Derivate erhält, wenn man monoacylierte bzw. motnocarbamidylierte o-Phenylendiamine mit N,N'-Bis-carboalkoxi-isothioharnstoffen umsetzt (Deutsche Patentanmeldungen P 19 55 749.4 und P 19 55 750.7 vom 6.11.1969). Die Ausbeute und die Reinheit der Produkte ist jedoch nicht immer befriedigend.It is the subject of an earlier law that fungicides are effective Phenylguanidine derivatives are obtained when monoacylated or motnocarbamidylated o-Phenylenediamines with N, N'-bis-carboalkoxy-isothioureas (German Patent applications P 19 55 749.4 and P 19 55 750.7 dated November 6, 1969). The yield and however, the purity of the products is not always satisfactory.
Es wurde nunmehr gefunden, daß man die bekannten Phenylguanidin-Derivate der Formel in welcher X für Halogen, Alkyl mit 1 bis 4 Kohienstoffatomen und Alkoxi mit 1 bis 4 Kohlenstoffatomen steht, n für 0, 1 und 2 steht, R für Wasserstoff und Alkyl mit 1 bis 4 Kohlenstoffatomen steht, R' für Alkyl mit 1 bis 12 Kohlenstoffatomen steht, für Wasserstoff, Alkyl mit 1 bis 18 Kohlenstoffatomen (gegebenenfalls substituiert durch Halogen, Cyan, Askoxi mit 1 bis 4 Kohlenstoffatomen, Alkoxioarbonyl mit 2 bis 5 Kohlenstoffatomen, Phenoxi, Haloge2lphenoxi, Alkoxiphenoxi), ferner für Cycloalkyl mit 5 bis 8 Kohlenstoffatomen, für Aralkyl (gegebenenfalls substituiert durch Halogen, Alkyl mit 1 bis 4 Kohlenstoffatomen oder Alkoxi mit 1 bis 4 Kohlenstoffatomen oder Alkoxi mit 1 bis 4 Kohlenstoffatomen), für l-Furyl und ferner für steht, wobei R"' für Wasserstoff und Alkyl mit 1 bis 4 Kohlenstoffatomen steht, Ritil für Wasserstoffatomen und für Alkyl mit 1 bis 18 Kohlenstoffatomen steht, wobei der Alkylrest gegebenenfalls substituiert sein kann durch Halogen, Cyan, Alkoxi mit bis zu 4 Kohlenstoffatomen, Alkoxicarbonyl mit bis zu 5 Kohlenstoffatomen, ferner für Cycloalkyl mit 5 bis 8 Kohlenstoffatomen, für Aralkyl (das gegebenenfalls im Arylteil durch Halogen, Niederalkyl und/oder Niederalkoxi substituiert sein kann), für Acyl mit bis zu 18 Kohlenstoffatomen (gegebenenfalls substituiert durch Halogen, Niederalkyl, Niederalkoxi), für Alkylsulfonyl mit bis zu 18 Kohlenstoffatomen, für Arylsulfonyl (gegebenenfalls substituiert durch Halogen,,Amino, Niederalkyl, Niederalkoxi) und für Dialkylamino mit bis zu 4 Kohlenstoffatomen steht, weiterhin R"' und R"" auch gemeinsam mit dem verbindenden Stickstoffatom für einen heterocyclischen Ring mit 4 bis 7 Kohlenstoffatomen stehen können, wobei der Ring noch gegebenenfalls Sauerstoff oder Schwefel als weitere Heteroatome enthalten kann, aus 2«Aminoanilin-Derivaten der Formel in welcher X, n, R und R" die oben angegebene Bedeutung haben und N,N'-Bis-carboalkyoxi-isothioharnstoff-S-alkyläthern der Formel in welcher R' die oben angegebene Bedeutung hat und R""' für Alkyl mit 1 bis 4 Kohlenstoffatomen steht, in besonders hoher Reinheit und verbesserter Ausbeute nur dann erhält, wenn man zu der in einem Verdünnungsmittel durchgeführten Reaktion als Katalysator organische oder anorganische Säuren in Mengen von 0,1 bis 20 Molprozent zusetzt.It has now been found that the known phenylguanidine derivatives of the formula in which X stands for halogen, alkyl with 1 to 4 carbon atoms and alkoxy with 1 to 4 carbon atoms, n stands for 0, 1 and 2, R stands for hydrogen and alkyl with 1 to 4 carbon atoms, R 'stands for alkyl with 1 to 12 Carbon atoms stands for hydrogen, alkyl with 1 to 18 carbon atoms (optionally substituted by halogen, cyano, askoxi with 1 to 4 carbon atoms, alkoxioarbonyl with 2 to 5 carbon atoms, phenoxy, haloge2lphenoxy, alkoxyphenoxy), furthermore for cycloalkyl with 5 to 8 carbon atoms, for aralkyl (optionally substituted by halogen, alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms), for l-furyl and furthermore for R "'stands for hydrogen and alkyl with 1 to 4 carbon atoms, ritil for hydrogen atoms and for alkyl with 1 to 18 carbon atoms, where the alkyl radical can optionally be substituted by halogen, cyano, alkoxy with up to 4 carbon atoms, alkoxicarbonyl with up to 5 carbon atoms, also for cycloalkyl with 5 to 8 carbon atoms, for aralkyl (which can optionally be substituted in the aryl part by halogen, lower alkyl and / or lower alkoxy), for acyl with up to 18 carbon atoms (optionally substituted by halogen, lower alkyl, Lower alkoxy), for alkylsulfonyl with up to 18 carbon atoms, for arylsulfonyl (optionally substituted by halogen, amino, lower alkyl, lower alkoxy) and for dialkylamino with up to 4 carbon atoms, furthermore R "'and R""also together with the connecting nitrogen atom may represent a heterocyclic ring having 4 to 7 carbon atoms, the ring also optionally being S may contain oxygen or sulfur as further heteroatoms, from 2 «aminoaniline derivatives of the formula in which X, n, R and R "have the meaning given above and N, N'-bis-carboalkyoxy-isothiourea-S-alkyl ethers of the formula in which R 'has the meaning given above and R ""' stands for alkyl having 1 to 4 carbon atoms, is only obtained in particularly high purity and improved yield when organic or inorganic acids are used as a catalyst for the reaction carried out in a diluent Adds amounts of 0.1 to 20 mole percent.
Das erfindungsgemäße Verfahren erweist sich als vorteilhaft, da die Reinheit der Produkte und die erzielten Ausbeuten wesentlich verbessert werden konnten.The inventive method proves to be advantageous because the The purity of the products and the yields achieved could be significantly improved.
Verwendet man o-Amino-acetanilid und N,N'-Bis-carbomethoxiisothioharnstoff-S-methyläther
als Ausgangsstoffe, so läßt sich der Reaktionsablauf durch folgendes Formelschema
wiedergeben:
Die als Ausgangsprodukte verwendeten 2-Aminoanilin-Derivate sind zum großen Teil bekannt (vgl. Beilsteins Handbuch der Organischen Chemie Band 13, Seite 20-32, Berlin 1930; Band 13, 1. Ergänzungswerk, Seite 8-10, Berlin 1933; Band 13, 2. Ergänzungswerk, Seite 14-23, Berlin-Göttingen-Heidelberg 1950). Sie können im übrigen durch Reduktion oder katalytische Hydrierung der entsprechenden Nitroverbindungen gewonnen werden.The 2-aminoaniline derivatives used as starting materials are for largely known (see Beilstein's Handbook of Organic Chemistry Volume 13, page 20-32, Berlin 1930; Volume 13, 1st supplementary work, pages 8-10, Berlin 1933; Volume 13, 2nd supplementary work, pages 14-23, Berlin-Göttingen-Heidelberg 1950). You can use the the rest by reduction or catalytic hydrogenation of the corresponding nitro compounds be won.
Die als Ausgangsstoffe verwendeten Isothioharnstoffäther sind durch die Formel (III) eindeutig definiert. In dieser Formel steht R' vorzugsweise für Methyl, Äthyl, Isopropyl und sec.-Butyl, R""' vorzugsweise für Methyl und Äthyl. Die Isothioharnstoffäther sind zum Teil bekannt (vgl. Olin und Dains, J. Amer. Chem. Soc. 52, 3326 (1930) und USA-Patentschrift 2 933 502), sie können im übrigen aus S-Alkyl-isothioharnstoffäthern und Chlorameisensäurealkylestern in Gegenwart äquivalenter Mengen Alkali gewonnen werden.The isothiourea ethers used as starting materials are through the formula (III) is clearly defined. In this formula, R 'preferably stands for Methyl, ethyl, isopropyl and sec-butyl, R "" 'preferably for methyl and ethyl. Some of the isothiourea ethers are known (cf. Olin and Dains, J. Amer. Chem. Soc. 52, 3326 (1930) and US Pat. No. 2,933,502), otherwise you can choose from S-alkyl isothiourea ethers and alkyl chloroformates in the presence of equivalent Amounts of alkali can be obtained.
Als Verdünnungsmittel kommen bei der Durchführung des erfindungsgemäßen Verfahrens alle polaren organischen Lösungsmittel infrage. Hierzu gehören vorzugsweise Alkohole, wie Methanol, Äthanol, Isopropanol sowie deren Gemische mit Wasser, Ketone, wie Aceton (auch mit Wasser gemischt), aber auch Äther, wie Dioxan oder Tetrahydrofuran.Suitable diluents when carrying out the invention Process all polar organic solvents in question. These preferably include Alcohols such as methanol, ethanol, isopropanol and their mixtures with water, ketones, like acetone (also mixed with water), but also ethers like dioxane or tetrahydrofuran.
Als Beispiele für die erfindungsgemäß als Katalysatoren verwendeten Säuren seien genannt: Salzsäure, Salpetersäure, Schwefelsäure, Ameisensäure, Essigsäure, p-Toluolsulfonsäure.As examples of those used as catalysts according to the invention Acids are: hydrochloric acid, nitric acid, sulfuric acid, formic acid, acetic acid, p-toluenesulfonic acid.
Die Reaktionstemperaturen können in einem größeren Bereich variiert werden. Im allgemeinen arbeitet man zwischen 50 und 1200C, vorzugsweise zwischen 60 und 10000.The reaction temperatures can be varied within a relatively wide range will. In general, between 50 and 1200C, preferably between 60 and 10000.
Bei der Durchführung des erfindungsgemäßen Verfahrens setzt man auf 1 Mol 2-Aminoanilin-Derivat 1 Mol Isothioharnstoffäther ein. Uberschüsse um bis zu 30 Gewichtsprozent an der einer oder anderen Substanz sind ohne wesentliche Ausbeuteverschlechterung möglich. Die Reaktion wird bevorzugt in einem siedenden Lösungsmittel durchgeführt, wobei Alkylmercaptan als Nebenprodukt entsteht. Die Endprodukte fallen beim Abkühlen des Reaktionsgemisches kristallin an und können durch Absaugen abgetrennt und gegebenenfalls durch Umkristallisieren bzw. Umlösen gereinigt werden. Herstellungsbeispiele Beispiel 1: 33 g (0,22 Mol) 2-Aminoacetanilid, 47,2 g (0,2 Mol) N,N'-Biscarbomethoxi-isothioharnstoff-S-methyl-äther und 2,6 g (0,015 Mol) p-Toluolsulfonsäure werden gemeinsam in 300 ccm Methanol wahrend 3 Stunden gekocht. Danach kühlt man auf OOC ab und saugt das Ausgefallene nach einigen Stunden ab. Man erhält nach dem Trocknen 55 g N-(2-Acetamido-phenyl)-N',"-bismethoxicarbonyl-guanidin vom Schmelzpunkt 1635oC. Die Ausbeute beträgt 89% der Theorie.When carrying out the process according to the invention, 1 mole of isothiourea ether is used for 1 mole of 2-aminoaniline derivative. Excesses of up to 30 percent by weight of one or the other substance are possible without any significant deterioration in the yield. The reaction is preferably carried out in a boiling solvent, with alkyl mercaptan being formed as a by-product. The end products are obtained in crystalline form when the reaction mixture cools and can be separated off by suction and, if necessary, purified by recrystallization or redissolution. Production examples Example 1: 33 g (0.22 mol) of 2-aminoacetanilide, 47.2 g (0.2 mol) of N, N'-biscarbomethoxy-isothiourea-S-methyl ether and 2.6 g (0.015 mol) of p-toluenesulfonic acid are combined boiled in 300 cc of methanol for 3 hours. Then you cool down to OOC and vacuum off the failed after a few hours. After drying, 55 g of N- (2-acetamido-phenyl) -N ', "- bismethoxicarbonyl-guanidine with a melting point of 1635 ° C. are obtained. The yield is 89% of theory.
Auf ähnliche Weise werden die folgenden Verbindungen erhalten: Beispiel Nr. Formel Schmp. (°C) Beispiel Nr. Formel Schmp. (°C) In a similar manner the following compounds are obtained: Example No. Formula m.p. (° C) Example no. Formula m.p. (° C)
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19712109454 DE2109454A1 (en) | 1971-02-27 | 1971-02-27 | Fungicidal n-(2-acylaminophenyl)-n,n-bis(alkoxycarbonyl)-guanidines - from 2-acrylaminoanilines and s-alkyl n,n-bis(alkoxycarbonyl) isothiazole |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19712109454 DE2109454A1 (en) | 1971-02-27 | 1971-02-27 | Fungicidal n-(2-acylaminophenyl)-n,n-bis(alkoxycarbonyl)-guanidines - from 2-acrylaminoanilines and s-alkyl n,n-bis(alkoxycarbonyl) isothiazole |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE2109454A1 true DE2109454A1 (en) | 1972-09-14 |
Family
ID=5800053
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19712109454 Pending DE2109454A1 (en) | 1971-02-27 | 1971-02-27 | Fungicidal n-(2-acylaminophenyl)-n,n-bis(alkoxycarbonyl)-guanidines - from 2-acrylaminoanilines and s-alkyl n,n-bis(alkoxycarbonyl) isothiazole |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE2109454A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2203631A1 (en) * | 1972-10-18 | 1974-05-17 | Bayer Ag | |
| FR2370727A1 (en) * | 1976-11-11 | 1978-06-09 | Bayer Ag | NEW DERIVATIVES OF O-PHENYLENEDIAMINE, THEIR PREPARATION PROCESS AND THE MEDICINAL PRODUCT CONTAINING THEM |
| WO2001002423A3 (en) * | 1999-07-07 | 2001-05-03 | Isis Pharmaceuticals Inc | 2'-guanidinyl-substituted oligonucleotides and gene expression modulation therewith |
-
1971
- 1971-02-27 DE DE19712109454 patent/DE2109454A1/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2203631A1 (en) * | 1972-10-18 | 1974-05-17 | Bayer Ag | |
| FR2370727A1 (en) * | 1976-11-11 | 1978-06-09 | Bayer Ag | NEW DERIVATIVES OF O-PHENYLENEDIAMINE, THEIR PREPARATION PROCESS AND THE MEDICINAL PRODUCT CONTAINING THEM |
| WO2001002423A3 (en) * | 1999-07-07 | 2001-05-03 | Isis Pharmaceuticals Inc | 2'-guanidinyl-substituted oligonucleotides and gene expression modulation therewith |
| US6534639B1 (en) | 1999-07-07 | 2003-03-18 | Isis Pharmaceuticals, Inc. | Guanidinium functionalized oligonucleotides and method/synthesis |
| US6593466B1 (en) | 1999-07-07 | 2003-07-15 | Isis Pharmaceuticals, Inc. | Guanidinium functionalized nucleotides and precursors thereof |
| US6914148B2 (en) | 1999-07-07 | 2005-07-05 | Isis Pharmaceuticals, Inc. | Guanidinium functionalized intermediates |
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