[go: up one dir, main page]

DE1088960B - Process for the preparation of amine addition salts of 2-mercapto-pyridine-1-oxides - Google Patents

Process for the preparation of amine addition salts of 2-mercapto-pyridine-1-oxides

Info

Publication number
DE1088960B
DE1088960B DEO6087A DEO0006087A DE1088960B DE 1088960 B DE1088960 B DE 1088960B DE O6087 A DEO6087 A DE O6087A DE O0006087 A DEO0006087 A DE O0006087A DE 1088960 B DE1088960 B DE 1088960B
Authority
DE
Germany
Prior art keywords
mercapto
pyridine
oxide
addition salts
preparation
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
Application number
DEO6087A
Other languages
German (de)
Inventor
Jack Bernstein
William A Lott
Kathryn A Losee
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Olin Corp
Original Assignee
Olin Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Olin Corp filed Critical Olin Corp
Publication of DE1088960B publication Critical patent/DE1088960B/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D213/00Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/89Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members with hetero atoms directly attached to the ring nitrogen atom

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pyridine Compounds (AREA)

Description

Verfahren zur Herstellung von Aminadditionss alzen von 2-Mercapto-pyridin-1-oxyden Die Erfindung betrifft die Herstellung von bestimmten Aminadditionssalzen von Säuren der allgemeinen Formel welche fungicide Stoffe darstellen; R bedeutet entweder ein Wasserstoff- oder Halogenatom oder einen niederen Alkyl- oder Alkoxyrest.Process for the preparation of amine addition salts of 2-mercapto-pyridine-1-oxides The invention relates to the preparation of certain amine addition salts of acids of the general formula which represent fungicides; R denotes either a hydrogen or halogen atom or a lower alkyl or alkoxy radical.

Das erfindungsgemäße Verfahren wird so durchgeführt, daß man ein 2-Mercapto-pyridin-1-oxyd der vorstehend genannten Konstitution mit einem Amin der allgemeinen Formel (höheres Alkyl) N \ R' in welcher R' und R" je ein Wasserstoffatom oder einen niedrigen Alkylrest bedeuten, in einem nahezu wasser freien organischen Lösungsmittel umsetzt und das Reaktionsprodukt abtrennt. Vorzugsweise verwendet man zur Umsetzung mit dem 2-Mercapto-pyridin-1-oxyd ein primäres höheres Alkylamin.The process according to the invention is carried out in such a way that a 2-mercaptopyridine-1-oxide of the above-mentioned constitution is mixed with an amine of the general formula (higher alkyl) NO' in which R 'and R "each denote a hydrogen atom or a lower alkyl radical, is reacted in a virtually anhydrous organic solvent and the reaction product is separated off. A primary higher alkylamine is preferably used for the reaction with the 2-mercaptopyridine-1-oxide.

Gegenüber den ebenfalls fungiciden Ausgangsstoffen besitzen die erfindungsgemäß erhaltenen Aminadditionssalze beachtliche Vorteile. Compared to the likewise fungicidal starting materials, those according to the invention have obtained amine addition salts have considerable advantages.

Während die Ausgangsverbindungen nur schlecht in organischen Lösungsmitteln, z. B. Benzol und Leuchtpetroleum, dispergiert werden können, sind die Aminadditionssalze in diesen Lösungsmitteln löslich. Solche organischen Lösungen lassen sich jedoch viel besser auf den Pflanzen versprühen als wäßrige Lösungen, und die Folge davon ist, daß dieselben Mengen des Fungicids für eine größere bepflanzte Fläche ausreichen und somit die Spritzkosten wesentlich erniedrigt werden. Ferner werden lokale hohe Konzentrationen auf den Pflanzen und somit Pflanzenvergiftungen vermieden. While the starting compounds are poor in organic solvents, z. B. benzene and kerosene, which can be dispersed, are the amine addition salts soluble in these solvents. Such organic solutions can, however spray much better on the plants than aqueous solutions, and the consequence of it is that the same amounts of the fungicide are sufficient for a larger planted area and thus the injection costs are significantly reduced. Furthermore, local high Avoid concentrations on the plants and thus plant poisoning.

Die Aminadditionssalze besitzen sowohl die baktericide Wirkung des Aminbestandteils als auch die fungicide Wirkung des Mercaptopyridins, d. h., sie sind sowohl gegen Bakterien als auch gegen Pilze anzuwenden. The amine addition salts have both the bactericidal effect of the Amine component as well as the fungicidal effect of mercaptopyridine, d. h., they are to be used against both bacteria and fungi.

Die erfindungsgemäß erhaltenen Verbindungen sind ferner viel stabiler als die Ausgangsstoffe. So hatte bei einem Vergleichstest das 2-Mercapto-pyridin-l-oxyd nach 22 Stunden bei Raumtemperatur in einem organischen Lösungsmittel jede fungicide Wirksamkeit verloren, während die mit Cetylamin gebildete Additionsverbindung unter denselben Bedingungen ihre Wirksamkeit nahezu vollständig beibehielt. The compounds obtained according to the invention are also much more stable than the starting materials. In a comparative test, for example, it had 2-mercapto-pyridine-1-oxide after 22 hours at room temperature in an organic solvent any fungicide Effectiveness lost while the addition compound formed with cetylamine under almost completely retained its effectiveness under the same conditions.

Die erfindungsgemäß erhaltenen Verbindungen sind gegen eine große Gruppe von Mikroorganismen wirksam. The compounds obtained according to the invention are against a large one Group of microorganisms effective.

Da die erfindungsgemäß erhaltenen Verbindungen ausgedehnte baktericide und fungicide Eigenschaften besitzen, können sie als Schutzmittel für eine Vielzahl von Produkten, als Mittel zur Verhütung von Stockflecken und als Sterilisations- und Desinfektionsmittel Verwendung finden. So sind sie z. B. als fungicide Pflanzenschutzmittel, beispielsweise gegen Peronospera, die auf Reben wächst, geeignet. Since the compounds obtained according to the invention have extensive bactericidal properties and possess fungicidal properties, they can be used as preservatives for a variety of products, as a means of preventing mold stains and as a sterilization and disinfectants are used. So they are z. B. as fungicidal pesticides, for example against Peronospera, which grows on vines, suitable.

Außerdem sind sie wertvolle chemotherapeutische Mittel, insbesondere Fungicide, und können zur Behandlung von Dermatophytosis pedis und zur Eindämmung oberflächlicher Pilzinfektionen der Haut und zugänglicher Schleimhäute Anwendung finden. They are also valuable chemotherapeutic agents, in particular Fungicide, and can be used to treat and contain dermatophytosis pedis superficial fungal infections of the skin and accessible mucous membranes Find.

Als 2-Mercapto-pyridin-l-oxyde kommen z. B. in Frage: 2-Mercapto-pyridin-i -oxyd, 3-Äthoxy-2-mercapto-pyridinl-oxyd, 2-Mercapto-3-methoxy-pyndin-l -oxyd, 5-Brom-2-mercapto-pyridin-1 -oxyd, 2-Mercapto-3-äthyl-pyridinl-oxyd, 2-Mercapto-4-methyl-pyridin-1 -oxyd, 2-Mercapto-5-methyl-pyridin-1 -oxyd, 2-Mercapto-6-methyl-pyridinl-oxyd und 2-Mercapto-6-propyl-pyridin- 1-oxyd (siehe z. B. Journ. Am. Chem. Soc., Bd. 72, S. 4362 ff. £1950j, betreffend die Herstellung von substituierten 2-Mercaptopyridin-l -oxyden). As 2-mercapto-pyridine-1-oxides come z. B. in question: 2-mercapto-pyridine-i oxide, 3-ethoxy-2-mercapto-pyridine-oxide, 2-mercapto-3-methoxy-pyndine-1-oxide, 5-bromo-2-mercapto-pyridine-1 oxide, 2-mercapto-3-ethyl-pyridine-oxide, 2-mercapto-4-methyl-pyridine-1-oxide, 2-mercapto-5-methyl-pyridine-1 oxide, 2-mercapto-6-methyl-pyridine-oxide and 2-mercapto-6-propyl-pyridine-1-oxide (please refer z. B. Journ. At the. Chem. Soc., Vol. 72, pp. 4362 ff. £ 1950j, concerning the production of substituted 2-mercaptopyridine-1-oxides).

Die folgenden Beispiele erläutern die Erfindung. The following examples illustrate the invention.

Beispiel 1 Eine Lösung von 1,27 g 2-Mercapto-pyndin-l-oxyd in 3 cm3 absolutem Alkohol wird zu einer Lösung von 2,41 g Cetylamin in 1 cm3 absolutem Alkohol zugegeben. Dann fügt man etwa 25 cm3 trockenen Äther hinzu, und nach Abkühlung und Kratzen der Gefäßwände erfolgt Kristallisation. Der etwa 2,7 g wiegende kristalline Feststoff, der bei etwa 78 bis 80"C schmilzt, ist das Cetylaminsalz von 2-Mercapto-pyridin-1 -oxyd (nach Umkristallisation aus Alkohol-Äther-Gemisch schmilzt die Verbindung bei etwa 79 bis 81"C). Example 1 A solution of 1.27 g of 2-mercapto-pyndine-1-oxide in 3 cm3 absolute alcohol becomes a solution of 2.41 g of cetylamine in 1 cm3 of absolute alcohol admitted. Then add about 25 cm3 of dry ether, and after cooling down and Crystallization occurs when the vessel walls are scratched. The crystalline weighs about 2.7 g Solid, which melts at about 78 to 80 "C, is the cetylamine salt of 2-mercapto-pyridine-1 oxide (after recrystallization from an alcohol-ether mixture, the compound melts at about 79 to 81 "C).

Bei Verwendung der äquivalenten Menge Octylamin an Stelle von Cetylamin im Beispiel 1 erhält man das Octylaminsalz von 2-Mercapto-pyridin-1 -oxyd. When using the equivalent amount of octylamine instead of cetylamine in Example 1, the octylamine salt of 2-mercapto-pyridine-1-oxide is obtained.

Beispiel 2 Eine Lösung von 1,27 g 2-Mercapto-pyridin-l-oxyd in 5 cm3 absolutem Alkohol wird zu 2,69 g Cetyl-dimethylamin zugegeben. Man fügt dann etwa 25 cm3 trockenen Äther hinzu, und nach Abkühlung und Kratzen der Gefäßwände erfolgt Kristallisation. Der etwa 2g wiegende und bei 62 bis 630 C schmelzende Feststoff ist das Cetyldimethyl-aminsalz von 2-Mercapto-pyridin-1 -oxyd. Nach Umkristallisation aus Alkohol-Äther-Gemisch beträgt der Schmelzpunkt 63 bis 64"C. Bei Verwendung der äquivalenten Menge von Lauryl-diäthyl-amin an Stelle von Cetyl-dimethyl-amin im Beispiel 2 erhält man das Lauryldiäthyl-aminsalz von 2-Mercapto-pyndin-l-oxyd. Example 2 A solution of 1.27 g of 2-mercapto-pyridine-1-oxide in 5 cm3 of absolute alcohol is added to 2.69 g of cetyldimethylamine. One then adds Add about 25 cm3 of dry ether, and after cooling and scraping the vessel walls crystallization occurs. The solid, which weighs about 2g and melts at 62 to 630 ° C is the cetyldimethylamine salt of 2-mercapto-pyridine-1-oxide. After recrystallization from an alcohol-ether mixture the melting point is 63 to 64 "C. When using the equivalent amount of lauryl diethyl amine instead of cetyl dimethyl amine im Example 2 gives the lauryl diethyl amine salt of 2-mercapto-pyndine-1-oxide.

Claims (1)

PATENTANSPRUCH: Verfahren zur Herstellung von Aminadditionssalzen von Säuren der allgemeinen Formel in welcher R ein Wasserstoff- oder Halogenatom oder einen niedrigen Alkyl- oder Alkoxyrest bedeutet, dadurch gekennteichttet, daß man ein 2-Mercaptopyridin-l-oxyd der genannten Konstitution mit einem Amin der allgemeinen Formel (höheres Alkyl) N-R'
in welcher R' und R" je ein Wasserstoffatom oder einen niedrigen Alkylrest darstellen, in einem nahezu wasserfreien organischen Lösungsmittel umsetzt und das Reaktionsprodukt abtrennt.
PATENT CLAIM: Process for the preparation of amine addition salts of acids of the general formula in which R denotes a hydrogen or halogen atom or a lower alkyl or alkoxy radical, characterized in that a 2-mercaptopyridine-1-oxide of the stated constitution with an amine of the general formula (higher alkyl) NO'
in which R 'and R "each represent a hydrogen atom or a lower alkyl radical, is reacted in a virtually anhydrous organic solvent and the reaction product is separated off.
In Betracht gezogene Druckschriften: Britische Patentschrift Nr. 679 382; Journ. Am. Chem. Soc., Bd. 72, S. 4362 bis 4364 (1950). Documents considered: British Patent No. 679,382; Journ. At the. Chem. Soc., Vol. 72, pp. 4362 to 4364 (1950).
DEO6087A 1953-05-19 1954-05-19 Process for the preparation of amine addition salts of 2-mercapto-pyridine-1-oxides Pending DE1088960B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US1088960XA 1953-05-19 1953-05-19

Publications (1)

Publication Number Publication Date
DE1088960B true DE1088960B (en) 1960-09-15

Family

ID=22324679

Family Applications (1)

Application Number Title Priority Date Filing Date
DEO6087A Pending DE1088960B (en) 1953-05-19 1954-05-19 Process for the preparation of amine addition salts of 2-mercapto-pyridine-1-oxides

Country Status (1)

Country Link
DE (1) DE1088960B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2833013A1 (en) * 1977-07-28 1979-02-15 Oreal NEW ALUMINUM-SULFUR COMPOUND, METHOD OF MANUFACTURING IT, AND MEANS OF CONTAINING THIS COMPOUND

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB679382A (en) * 1949-02-11 1952-09-17 Monsanto Chemicals Improvements in or relating to quaternary ammonium compounds

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB679382A (en) * 1949-02-11 1952-09-17 Monsanto Chemicals Improvements in or relating to quaternary ammonium compounds

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2833013A1 (en) * 1977-07-28 1979-02-15 Oreal NEW ALUMINUM-SULFUR COMPOUND, METHOD OF MANUFACTURING IT, AND MEANS OF CONTAINING THIS COMPOUND

Similar Documents

Publication Publication Date Title
DE1695274A1 (en) Process for the preparation of new imidazole carboxylates
CH380734A (en) Process for the preparation of new s-triazine derivatives
CH641010A5 (en) PARASITENBEKAEMPFUNGSMITTEL FOR controlling harmful microorganisms.
DE1174018B (en) Preparations for combating harmful microorganisms
DE2641836B1 (en) Alkylated polyamines, their production and use as microbicides
AT334134B (en) FIGHTING FUNGI PEST
DE2635389C2 (en) Preservatives and disinfectants
DE1088960B (en) Process for the preparation of amine addition salts of 2-mercapto-pyridine-1-oxides
CH635227A5 (en) Parasitenbekaempfungsmittel.
DE2244778C3 (en) 1 -n-dodecylaminomethyl-2-aminocyclopentane, its production and use as a microbicidal active ingredient
DE1034645B (en) Process for the production of neutral sulfuric acid esters
DE1668616B2 (en) BISDITHIOCARBAMTE, PROCESS FOR THEIR PRODUCTION AND FUNGICIDAL AGENT CONTAINING THIS
EP0043125B1 (en) Aluminium-organic compounds, preparation of these compounds, cosmetic compositions containing these compounds as active agents and use of these compositions to combat and prevent seborrhoea
DE2144125A1 (en) Dithiocarboamic acid salts or urea derivs - from urea derivs and dithio-carbamic acid salts, fungicides, microbicides
DE2744353A1 (en) HYDANTOIN DERIVATIVES, THE PROCESS FOR THEIR PRODUCTION AND THEIR USE
DE2508420A1 (en) QUATERNAERE IMIDAZOLIUM JOINTS
AT268271B (en) Process for the preparation of new imidazole carboxylates and their salts
DE953125C (en) Agent for combating microorganisms such as fungi, bacteria and protozoa
DE2247370C3 (en) 1,3,3-Trimethyl-1-noctylaminomethyl-5-n-octylamino-cyclohexane, process for their preparation and their use as a microbicidal active ingredient
DE1593592C (en) Process for the preparation of adducts of organic mercury compounds which are soluble or dispersible in water or water-miscible solvents and their use as fungicides and bactericides
DE1966863C3 (en) N, N'-bis [(I -formamido-2 ^, 2.trichlor) ethyl] ethylenediamines, and pesticides which contain these compounds as active ingredients
DE1169948B (en) Process for the production of antibacterially active N, N'-alkylene-1, 1'-alkylene-bis- (4-aminochinolinium halides)
AT353984B (en) MICROBICIDAL PREPARATION
DE1140578B (en) Process for the preparation of quaternary ammonium salts of 2-mercaptopyridine-1-oxides
DE2144123A1 (en) Dithiocarbamic acid heavy metal salts and guanidines - complexes - fungicides and microbicides