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EP0000377A1 - Process for the preparation of chromone derivatives, new chromone derivatives and their use as plant-protecting agents - Google Patents

Process for the preparation of chromone derivatives, new chromone derivatives and their use as plant-protecting agents Download PDF

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Publication number
EP0000377A1
EP0000377A1 EP78100318A EP78100318A EP0000377A1 EP 0000377 A1 EP0000377 A1 EP 0000377A1 EP 78100318 A EP78100318 A EP 78100318A EP 78100318 A EP78100318 A EP 78100318A EP 0000377 A1 EP0000377 A1 EP 0000377A1
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EP
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Prior art keywords
chromon
carboxy
carboxymethyl
carbo
hydroxyacetophenone
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EP78100318A
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German (de)
French (fr)
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EP0000377B1 (en
Inventor
Hans-Joachim Dr. Kabbe
Paul-Ernst Dr. Frohberger
Peter Dr. Roessler
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Bayer AG
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
    • C07D311/24—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 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 in position 2

Definitions

  • the present invention relates to a new, chemically peculiar process for the production of new chromone derivatives and their use as crop protection agents.
  • chromones can also be prepared from o-acylphenols and carboxylic acid derivatives in a ratio of 1: 1 (cf. P. Karrer, "Textbook of Organic Chemistry”. 13th edition, page 584, Georg Thieme Verlag, Stuttgart (1959)).
  • zinc ethylenebis-dithiocarbamidate is known as a standard preparation with worldwide distribution (from R. Wegler, "Chemistry of Plant Protection Products and Pest Control", Volume 4, page 139, Springer-Verlag, Berlin / Heidelberg / New York (1977)). At low application rates, however, the effect is not always satisfactory.
  • the new compounds of formula (I) have fungicidal properties; they also inhibit the development of arthropods. They are therefore of interest as pesticides.
  • R , R 2 also represent optionally substituted cycloalkyl and cycloalkenyl radicals having 3 to 8, preferably having 4 to 6, carbon atoms, such as, for example, cyclobutyl and in particular cyclopentyl and cyclohexyl.
  • Aryl radicals which may be substituted may be those having 6 to 10 carbon atoms, such as phenyl and naphthyl, preferably phenyl.
  • Suitable substituted aralkyl radicals are those having 7 to 18 carbon atoms, the aliphatic part of which contains 1 to 8, preferably 1 to 4, carbons and the aromatic part of which represents a carbocyclic radical having 6 to 10 carbon atoms.
  • the following aralkyl radicals may be mentioned by way of example: benzyl, phenylethyl, phenylpropyl, phenylbutyl, naphthylmethyl and naphthylethyl, preferably benzyl.
  • Preferred alkoxy groups are those with up to 4 carbon atoms, such as methoxy, xthoxy, propoxy, isopropoxy, butoxy, isobutoxy and tert-butoxy.
  • Preferred aryloxy groups are those with 6 or 10 carbon atoms, such as phenoxy and naphthoxy.
  • Preferred aralkoxy groups are those having 7 to 10 carbon atoms, such as benzyloxy, phenylethoxy, phenylpropoxy, phenylisopropoxy, phenylbutoxy, phenylisobutoxy and phenyl tert-butoxy.
  • Preferred alkoxycarbonyl groups are those with up to 4 carbon atoms in the alkyl radical, such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl.
  • Preferred dialkylamino groups are those with up to 3 carbon atoms in the alkyl radical, such as dimethylamino, diethylamino, and diisopropylamino, called. It is also possible for the two alkyl radicals of the dialkylamino group to be closed to form a ring, such as, for example, pyrrolidinyl, piperidinyl.
  • Halogens are fluorine, chlorine, bromine and iodine, preferably chlorine and bromine.
  • the radicals R and R 1 can in particular form a carbocyclic or heterocyclic five- or six-membered ring, such as, for example, a cyclopentene, cyclohexene, benzene, furan, dihydrofuran, thiophene, with the two carbon atoms of the benzene ring on which they are seated -, Dihydrothiophene, pyran, dihydropyran, pyridine or dioxole ring.
  • a carbocyclic or heterocyclic five- or six-membered ring such as, for example, a cyclopentene, cyclohexene, benzene, furan, dihydrofuran, thiophene, with the two carbon atoms of the benzene ring on which they are seated -, Dihydrothiophene, pyran, dihydropyran, pyridine or dioxole ring.
  • Substituents which do not change under the reaction conditions are suitable as substituents of the alkyl, cycloalkyl, aryl, aralkyl, alkoxy, aralkoxy, alkoxycarbonyl and dialkylamino groups of the radicals R to R 2 .
  • substituents of the alkyl, cycloalkyl, aryl, aralkyl, alkoxy, aralkoxy, alkoxycarbonyl and dialkylamino groups of the radicals R to R 2 examples include the halogens, such as fluorine, chlorine, bromine and iodine and the cyano group, furthermore the alkoxy and alkoxycarbonyl group with up to 4 and - if the substituents on ring systems are concerned - the alkyl and alkoxycarbonylalkyl groups. Group with up to 4 carbon atoms.
  • dialkylamino group with a total of up to 6, preferably up to 2, carbon atoms, then
  • the glyoxylic acid derivatives of the formula (III) are also required as starting compounds.
  • Z is preferably monovalent or divalent cations of alkali and alkaline earth metals, and ONO for the ammonium cation and M, di- and Trialkylamnonium cations.
  • the alkyl radicals preferably contain up to 2 carbon atoms.
  • Secondary amines are preferred as such, in particular cyclic amines such as pyrrolidine, also piperidine, N-methylpiperazine, morpholine, but also open-chain amines such as dimethylamine and diethylamine.
  • Secondary amines are preferred as such, in particular cyclic amines such as pyrrolidine, also piperidine, N-methylpiperazine, morpholine, but also open-chain amines such as dimethylamine and diethylamine.
  • the compounds mentioned are generally known.
  • the inventive process may at a temperature of -30 to + 150 ° C, preferably from 20 to 80 o C, to be performed.
  • the o-hydroxycarbonyl compounds and the salt of glyoxylic acid in stoichiometric amounts ie in a ratio of 1: 2.
  • a small excess of a component, in particular the glyoxylic acid salt is used (for example up to a molar ratio of 1: 2.5).
  • the amount of the amine used is not critical. In general, 0.05 to 1.5, preferably 0.1 to 1 mol of the amine, based on 1 mol of the o-hydroxycarbonyl compound, is used. If the o-hydroxyacetophenones are substituted by acidic groups such as carboxy groups, it may be expedient to neutralize the acidic groups with an excess of the amine.
  • the esterification of the dicarboxylic acids obtained can be carried out, for example, in a customary manner by stirring the dicarboxylic acid in 4 to 100, preferably 10 to 50 times the molar amount of alcohol of the formula R 3 --OH, with an acid such as conc. Added sulfuric acid or saturated with hydrogen chloride gas and warmed to temperatures from 60 to 120 ° C for a few hours.
  • the mixture of the dicarboxylic acid with the alcohol can also be mixed with at least twice the molar amount, based on the dicarboxylic acid, of a dehydrating agent, such as inorganic acid halides, for example thionyl chloride or phosphorus oxychloride.
  • salts of the dicarboxylic acids can also be reacted with at least twice the molar amount of an alkyl halide in a solvent such as dimethyl sulfoxide or dimethylformamide.
  • the active compounds according to the invention have a good fungitoxic effect. They do not damage crops in the concentrations necessary to control fungi. For these reasons, they are suitable for use as crop protection agents for combating fungi. Fungitoxic agents are used in crop protection to combat Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Bsidiomycetes, Deuteromycetes.
  • the active compounds according to the invention can be used against parasitic fungi and bacteria which attack above-ground parts of plants or attack the plants from the ground, and against seed-borne pathogens.
  • the good tolerance to plants allows use against fungal plant diseases by treating the standing crop or individual parts of it or the seed or the crop soil.
  • the active. substances are particularly effective against powdery mildew.
  • the active compounds according to the invention can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, pastes and granules. These are manufactured in a known manner, e.g. B. by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents.
  • extenders that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents.
  • organic solvents can also be used as auxiliary solvents.
  • liquid solvents aromatics, such as xylene, toluene, benzene or alkylnaphthalenes, chlorinated aroses or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, Chloroethylene or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. B.
  • Liquefied gaseous extenders or carriers mean those liquids which are gaseous at normal temperature and pressure, e.g. B.
  • aerosol propellants such as dichlorodifluoromethane or trichlorofluoromethane; as solid carriers: natural rock flour, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock meals, such as highly disperse silica, aluminum oxide and silicates; as an emulsifier; nonionic and anionic emulsifiers, such as polyoxyethylene photo acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ether, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; as a dispersant: e.g. B. lignin sulfite and methyl cellulose.
  • natural rock flour such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic
  • the formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
  • the active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. They are used in the usual way, e.g. by spraying, spraying, misting, scattering, dusting, pouring, dry pickling, slurry pickling (slurry pickling), wet pickling and wet pickling.
  • the active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges.
  • the active substance concentration of the use forms can be from 0.0000001 to 100% by weight of active substance, preferably between 0.01 and 10% by weight.
  • active compound 10 mg to 10 g, preferably 100 mg to 3 q, are generally used per kilogram of seed.
  • active substance concentrations of 1 to 1000 g of active substance per m 3 of soil, preferably 10 to 200 g per m 3 , are required at the location of the expected action.
  • the compounds according to the invention inhibit the development of arthropods (arthrophodes).
  • active compound 2 parts by weight of active compound are mixed with the stated amount of solvent, emulsifier and enough water to form a 1% mixture which is diluted with water to the desired concentration.
  • test animals are such that an amount of active ingredient is obtained in ppm ( "parts p ro million") on the leaves, fed with leaves of the feed plants, which are provided with a uniform spray coating of the active ingredient mixture of the chosen concentration, to the development of the imago.
  • active compound 0.25 part by weight of active compound is taken up in 25 parts by weight of dimethylformamide and 0.06 part by weight of emulsifier (alkyl aryl polyglycol ether), and 975 parts by weight of water are added.
  • emulsifier alkyl aryl polyglycol ether
  • the single-leafed barley young plants of the Amsel variety are sprayed with the preparation of active compound as dewy. After drying, the barley plants are dusted with spores from Erysiphe graminis var. Hordei.
  • the stocking of the plants with mildew pustules is evaluated.
  • the degree of infestation is expressed as a percentage of the infestation of the untreated control plants. O% means no infection and 100% means the same degree of infection as in the untreated control. The lower the mildew infestation, the more effective the active ingredient.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pyrane Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Die Verbindungen der Formel <IMAGE> in welcher R, R¹ und R² gleich oder verschieden, für Wasserstoff, gegebenenfalls substituiertes Alkyl, Alkenyl, Cycloalkyl, Cycloalkenyl, Aralkyl, Aryl, ferner für Halogen, Hydroxy, Alkoxy, Aryloxy, Aralkoxy, Alkoxycarbonyl, Cyan und/oder Dialkylamino stehen, und weiterhin zwei Reste R und R¹ zusammen mit zwei Kohlenstoffatomen des Benzolringsystems einen carbocyclischen oder heterocyclischen 5- oder 6-Ring bilden können, und R³ für Wasserstoff, gegebenenfalls substituiertes Alkyl, Alkenyl, Cycloalkyl, Cycloalkenyl oder Aralkyl steht, werden erhalten, wenn man o-Hydroxy-acetophenone mit Glyoxylsäure-Derivaten in Gegenwart von basischen Verbindungen umsetzt, und noch gegebenenfalls die dabei erhaltenen Carbonsäuren in an sich bekannter Weise in die entsprechenden Ester überführt. Die erfindungsgemässen Wirkstoffe weisen eine fungitoxische Wirkung auf. Aus diesen Gründen sind sie für den Gebrauch als Pflanzenschutzmittel zur Bekämpfung von Pilzen geeignet. Die Wirkstoffe sind besonders wirksam gegen Getreidemehltau und hemmen ferner die Entwicklung von Gliederfüsslern (Arthrophoden).The compounds of the formula <IMAGE> in which R, R¹ and R² are the same or different, for hydrogen, optionally substituted alkyl, alkenyl, cycloalkyl, cycloalkenyl, aralkyl, aryl, furthermore for halogen, hydroxy, alkoxy, aryloxy, aralkoxy, alkoxycarbonyl, cyan and / or dialkylamino, and furthermore two radicals R and R¹ together with two carbon atoms of the benzene ring system can form a carbocyclic or heterocyclic 5- or 6-ring, and R³ represents hydrogen, optionally substituted alkyl, alkenyl, cycloalkyl, cycloalkenyl or aralkyl, are obtained if o-hydroxy-acetophenones are reacted with glyoxylic acid derivatives in the presence of basic compounds, and, if appropriate, the carboxylic acids obtained are converted into the corresponding esters in a manner known per se. The active substances according to the invention have a fungitoxic effect. For these reasons, they are suitable for use as crop protection agents for combating fungi. The active ingredients are particularly effective against powdery mildew and also inhibit the development of arthropods (arthrophodes).

Description

Die vorliegende Erfindung betrifft ein neues, chemisch eigenartiges Verfahren zur Herstellung von neuen Chromon-Derivaten sowie ihre Verwendung als Pflanzenschutzmittel.The present invention relates to a new, chemically peculiar process for the production of new chromone derivatives and their use as crop protection agents.

Es ist bereits bekannt, daß aromatische Aldehyde in Gegenwart von Natronlauge mit o-Hydroxyacetophenonen zu 2-Phenyl-chromanonen reagieren (Elderfield, "Heterocyclic Compounds", Vol. 2, Seite 347), ferner ist noch bekannt, daß man auch aliphatische Aldehyde mit o-Hydroxyacetophenonen zu den entsprechenden 2-Alkylehromanonen umsetzen kann (vgl. DT-OS 2 535 338 LLe A 16 634]). In beiden Fällen reagieren o-Hydroxyacetophenon und Aldehyd im Molverhältnis 1:1. Weiterhin ist noch bekannt, daß man aus o-Acylphenolen und Carbonsaure-Derivaten ebenfalls im Verhältnis 1:1 Chromone herstellen kann (vgl. P. Karrer, "Lehrbuch der Organischen Chemie". 13. Auflage, Seite 584, Georg Thieme Verlag, Stuttgart (1959)).It is already known that aromatic aldehydes react with o-hydroxyacetophenones to give 2-phenyl-chromanones in the presence of sodium hydroxide solution (Elderfield, "Heterocyclic Compounds", Vol. 2, page 347). It is also known that aliphatic aldehydes are also used can convert o-hydroxyacetophenones to the corresponding 2-alkylhromanones (cf. DT-OS 2 535 338 LLe A 16 634]). In both cases, o-hydroxyacetophenone and aldehyde react in a molar ratio of 1: 1. Furthermore, it is also known that chromones can also be prepared from o-acylphenols and carboxylic acid derivatives in a ratio of 1: 1 (cf. P. Karrer, "Textbook of Organic Chemistry". 13th edition, page 584, Georg Thieme Verlag, Stuttgart (1959)).

Als Pflanzenschutzmittel mit fungizider Wirkung ist als Standard-Präparat mit weltweiter Verbreitung Zink-äthylenbis-dithiocarbamidat bekannt (vql. R. Wegler, "Chemie der Pflanzenschutz- und Schädlingsbekämpfungsmittel", Band 4, Seite 139, Springer-Verlag, Berlin/Heidelberg/New York (1977)). Bei niedrigen Aufwandmengen ist die Wirkung jedoch nicht immer befriedigend.As a plant protection product with a fungicidal action, zinc ethylenebis-dithiocarbamidate is known as a standard preparation with worldwide distribution (from R. Wegler, "Chemistry of Plant Protection Products and Pest Control", Volume 4, page 139, Springer-Verlag, Berlin / Heidelberg / New York (1977)). At low application rates, however, the effect is not always satisfactory.

Wirkstoffe, die die Metamorphose von Arthropoden hemmen, sind erst seit jüngerer Zeit im Pflanzenschutz von Interesse. Zu nennen ist hier z.B. das 2,2-Dimethyl-6-methoxy- benzopyran (Chem. Eng. News 54, 19 - 20 (1976)).Active substances that inhibit the metamorphosis of arthropods have only recently been of interest in crop protection. To be mentioned here is e.g. 2,2-dimethyl-6-methoxybenzopyran (Chem. Eng. News 54, 19-20 (1976)).

Es wurde gefunden, daß man die neuen Chromon-Derivate der allgemeinen Formel

Figure imgb0001
in welcher

  • R, R 1 und R2 gleich oder verschieden sein können und für Wasserstoff, gegebenenfalls substituiertes Alkyl, Alkenyl, Cycloalkyl, Cycloalkenyl, Aralkyl, Aryl, ferner für Halogen, Hydroxyl, Alkoxy, Aryloxy, Aralkoxy, Alkoxycarbonyl, Cyan und/oder Dialkylamino stehen, und weiterhin zwei Reste
  • R und R1 zusammen mit zwei Kohlenstoffatomen des Benzolringsystems einen carbocyclisehen oder heterocyclischen 5- oder 6-Ring bilden können, und
  • R 3 für Wasserstoff, gegebenenfalls substituiertes Alkyl, Alkenyl, Cycloalkyl, Cycloalkenyl oder Aralkyl steht, in einfacher Weise erhält, wenn man o-Hydroxyacetophenone der allgemeinen Formel
    Figure imgb0002
    in welcher
  • R, R1 und R2 die oben angegebene Bedeutung haben, mit Glyoxylsäure-Derivaten der allgemeinen Formel
    Figure imgb0003
    in welcher
  • Z für ein Kation steht, in Gegenwart von basischen Verbindungen umsetzt, und noch gegebenenfalls die dabei erhaltenen Carbonsäuren (Verbindungen der Formel (I), wobei R3 für Wasserstoff steht) in an sich bekannter Weise in die entsprechenden Ester überführt (Verbindungen der Formel (I), wobei R für gegebenenfalls substituiertes Alkyl, Alkenyl, Cycloalkyl, Cycloalkenyl oder Aralkyl steht).
It has been found that the new chromone derivatives of the general formula
Figure imgb0001
 in which
  • R , R 1 and R 2 may be the same or different and represent hydrogen, optionally substituted alkyl, alkenyl, cycloalkyl, cycloalkenyl, aralkyl, aryl, furthermore halogen, hydroxyl, alkoxy, aryloxy, aralkoxy, alkoxycarbonyl, cyano and / or dialkylamino , and two remains
  • R and R 1 together with two carbon atoms of the benzene ring system can form a carbocyclic or heterocyclic 5- or 6-ring, and
  • R 3 represents hydrogen, optionally substituted alkyl, alkenyl, cycloalkyl, cycloalkenyl or aralkyl, is obtained in a simple manner if o-hydroxyacetophenones of the general formula are obtained
    Figure imgb0002
     in which
  • R, R 1 and R 2 have the meaning given above, with glyoxylic acid derivatives of the general formula
    Figure imgb0003
     in which
  • Z stands for a cation, in the presence of basic compounds, and optionally also the carboxylic acids obtained in this way (compounds of the formula (I), where R 3 stands for hydrogen) in converted into the corresponding esters in a manner known per se (compounds of the formula (I), where R represents optionally substituted alkyl, alkenyl, cycloalkyl, cycloalkenyl or aralkyl).

Die neuen Verbindungen der Formel (I) besitzen fungizide Eigenschaften; ferner hemmen sie die Entwicklung von Arthropoden. Sie sind daher als Pflanzenschutzmittel von Interesse.The new compounds of formula (I) have fungicidal properties; they also inhibit the development of arthropods. They are therefore of interest as pesticides.

Es ist als ausgesprochen überraschend zu bezeichnen, daß die o-Hydroxyacetophenone der Formel (II) mit den Glyoxylsäure-Derivaten der Formel (III) in einer einfachen und überschaubaren Reaktion die Chromon-Derivate der Formel (I) ergeben und keine Chromanon-Verbindungen entstehend Das Auffinden der neuen Reaktion stellt eine Bereicherung der Technik dar. Von praktischem Interesse ist, daß die neuen Verbindungen als Pflanzenschutzmittel verwendet werden können.It can be described as extremely surprising that the o-hydroxyacetophenones of the formula (II) with the glyoxylic acid derivatives of the formula (III) give the chromone derivatives of the formula (I) in a simple and manageable reaction and no chromanone compounds are formed Finding the new reaction is an enrichment of the technology. It is of practical interest that the new compounds can be used as crop protection agents.

Setzt man o-Hydroxyacetophenon mit dem Natriumsalz der Glyoxylsäure in Gegenwart von Pyrrolidin um und verestert die dabei erhaltene Dicarbonsäure anschließend mit Methanol, so kann der Reaktionsablauf durch das folgende Reaktionsschema wiedergegeben werden:

Figure imgb0004
If o-hydroxyacetophenone is reacted with the sodium salt of glyoxylic acid in the presence of pyrrolidine and the resulting dicarboxylic acid is then esterified with methanol, the course of the reaction can be represented by the following reaction scheme:
Figure imgb0004

In der Formel (II) stehen R, R1 und R2 vorzugsweise für Wasserstoff und für gegebenenfalls substituiertes, geradkettiges oder verzweigtes Alkyl mit bis zu 8, bevorzugt bis zu 2 Kohlenstoffatomen, ferner für geradkettiges oder verzweigtes Alkenyl mit einer oder mehreren Doppelbindungen und bis zu 8 Kohlenstoffatomen, vorzugsweise bis zu 3 Kohlenstoffatomen und einer Doppelbindung. Als Alkyl- bzw. Alkenyl-Reste seien beispielsweise genannt:

  • Methyl, Äthyl, Propyl, Isopropyl, Butyl, Isobutyl, tert.-Butyl, Hexyl, Buten-(3)-yl und 4-Methyl-penten-(3)-yl.
In the formula (II), R, R 1 and R 2 preferably represent hydrogen and optionally substituted, straight-chain or branched alkyl having up to 8, preferably up to 2 carbon atoms, furthermore straight-chain or branched alkenyl having one or more double bonds and bis to 8 carbon atoms, preferably up to 3 carbon atoms and a double bond. Examples of alkyl or alkenyl radicals are:
  • Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, butene- (3) -yl and 4-methyl-penten- (3) -yl.

R, Rund R2 stehen weiterhin für gegebenenfalls substituierte Cycloalkyl- und Cycloalkenyl-Reste mit 3 bis 8, bevorzugt mit 4 bis 6 Kohlenstoffatomen, wie beispielsweise Cyclobutyl und insbesondere Cyclopentyl und Cyclohexyl. R , R 2 also represent optionally substituted cycloalkyl and cycloalkenyl radicals having 3 to 8, preferably having 4 to 6, carbon atoms, such as, for example, cyclobutyl and in particular cyclopentyl and cyclohexyl.

Als gegebenenfalls substituierte Arylreste seien solche mit 6 bis 10 Kohlenstoffatomen genannt, wie Phenyl und Naphthyl, bevorzugt Phenyl.Aryl radicals which may be substituted may be those having 6 to 10 carbon atoms, such as phenyl and naphthyl, preferably phenyl.

Als gegebenenfalls substituierte Aralkylreste kommen beispielsweise solche mit 7 bis 18 Kohlenstoffatomen, deren aliphatischer Teil 1 bis 8, bevorzugt 1 bis 4, Kohlenstoffe enthält und deren aromatischer Teil einen carbocyclischen Rest mit 6 bis 10 Kohlenstoffatomen darstellt, in Frage. Beispielhaft seien die folgenden Aralkylreste genannt: Benzyl, Phenyläthyl, Phenylpropyl, Phenylbutyl, Naphthylmethyl und Naphthyläthyl, bevorzugt Benzyl.Examples of suitable substituted aralkyl radicals are those having 7 to 18 carbon atoms, the aliphatic part of which contains 1 to 8, preferably 1 to 4, carbons and the aromatic part of which represents a carbocyclic radical having 6 to 10 carbon atoms. The following aralkyl radicals may be mentioned by way of example: benzyl, phenylethyl, phenylpropyl, phenylbutyl, naphthylmethyl and naphthylethyl, preferably benzyl.

Als bevorzugte Alkoxygruppen seien solche mit bis zu 4 Kohlenstoffatomen, wie Methoxy, Xthoxy, Propoxy, Isopropoxy, Butoxy, Isobutoxy und tert.-Butoxy,genannt.Preferred alkoxy groups are those with up to 4 carbon atoms, such as methoxy, xthoxy, propoxy, isopropoxy, butoxy, isobutoxy and tert-butoxy.

Als bevorzugte Aryloxygruppen seien solche mit 6 oder 10 Kohlenstoffatomen, wie Phenoxy und Naphthoxy, genannt.Preferred aryloxy groups are those with 6 or 10 carbon atoms, such as phenoxy and naphthoxy.

Als bevorzugte Aralkoxygruppen seien solche mit 7 bis 10 Kohlenstoffatomen, wie Benzyloxy, Phenyläthoxy, Phenylpropoxy, Phenylisopropoxy, Phenylbutoxy, Phenylisobutoxy und Phenyl-tert.-butoxy, genannt.Preferred aralkoxy groups are those having 7 to 10 carbon atoms, such as benzyloxy, phenylethoxy, phenylpropoxy, phenylisopropoxy, phenylbutoxy, phenylisobutoxy and phenyl tert-butoxy.

Als bevorzugte Alkoxycarbonylgruppen seien solche mit bis zu 4 Kohlenstoffatomen im Alkylrest, wie Methoxycarbonyl, Äthoxycarbonyl, Propoxycarbonyl, Isopropoxycarbonyl, genannt.Preferred alkoxycarbonyl groups are those with up to 4 carbon atoms in the alkyl radical, such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl.

Als bevorzugte Dialkylaminogruppan seien solche mit bis zu 3 Kohlenstoffatomen im Alkylrest, wie Dimethylamino, Diäthylamino, und Diisopropylamino, qenannt. Es ist auch möglich, daß die beiden Alkylreste der Dialkylaminogruppe zu einem Ring geschlossen sind, wie beispielsweise Pyrrolidinyl, Piperidinyl.Preferred dialkylamino groups are those with up to 3 carbon atoms in the alkyl radical, such as dimethylamino, diethylamino, and diisopropylamino, called. It is also possible for the two alkyl radicals of the dialkylamino group to be closed to form a ring, such as, for example, pyrrolidinyl, piperidinyl.

Als Halogene seien Fluor, Chlor, Brom und Jod, bevorzugt Chlor und Brom genannt.Halogens are fluorine, chlorine, bromine and iodine, preferably chlorine and bromine.

Die Reste R und R1 können insbesondere mit den beiden Kohlenstoffatomen des Benzolrings, an dem sie sitzen, einen carbocyclischen oder heterocyclischen fünf- oder sechsgliedrigen Ring bilden, wie z.B. einen Cyclopenten-, Cyclohexen-, Benzol-, Furan-, Dihydrofuran-, Thiophen-, Dihydrothiophen-, Pyran-, Dihydropyran-, Pyridin-oder Dioxolen-Ring.The radicals R and R 1 can in particular form a carbocyclic or heterocyclic five- or six-membered ring, such as, for example, a cyclopentene, cyclohexene, benzene, furan, dihydrofuran, thiophene, with the two carbon atoms of the benzene ring on which they are seated -, Dihydrothiophene, pyran, dihydropyran, pyridine or dioxole ring.

Als Substituenten der Alkyl-, Cycloalkyl-, Aryl-, Aralkyl-, Alkoxy-, Aralkoxy-, Alkoxycarbonyl- und Dialkylamino-Gruppen der Reste R bis R2 kommen Substituenten in Frage, die unter den Reaktionsbedingungen nicht verändert werden. Beispielsweise seien die Halogene, wie Fluor, Chlor, Brom und Jod und die Cyangruppe genannt, ferner die Alkoxy- und Alkoxycarbonyl-Gruppe mit bis zu 4, und - sofern es sich um Substituenten an Ringsystemen handelt - noch die Alkyl- und die Alkoxycarbonylalkyl-Gruppe mit bis zu 4 Kohlenstoffatomen. Ferner sind als weitere Zweitsubstituenten noch die Dialkylamino-Gruppe mit insgesamt bis zu 6, vorzugsweise bis zu 2 Kohlenstoffatomen zu nennen, sodann die Carboxyl-Gruppe und der Phenyl-Rest.Substituents which do not change under the reaction conditions are suitable as substituents of the alkyl, cycloalkyl, aryl, aralkyl, alkoxy, aralkoxy, alkoxycarbonyl and dialkylamino groups of the radicals R to R 2 . Examples include the halogens, such as fluorine, chlorine, bromine and iodine and the cyano group, furthermore the alkoxy and alkoxycarbonyl group with up to 4 and - if the substituents on ring systems are concerned - the alkyl and alkoxycarbonylalkyl groups. Group with up to 4 carbon atoms. Also to be mentioned as further second substituents are the dialkylamino group with a total of up to 6, preferably up to 2, carbon atoms, then the carboxyl group and the phenyl radical.

Die o-Hydroxy-aryl-carbonylverbindungen, die für das erfindungsgemäße Verfahren Verwendung finden können, sind bekannt (vgl. Beilstein, Handbuch der Organischen Chemie, H8, Seite 85 ff.). Beispielsweise sieen genannt:

  • o-Hydroxyacetophenon 3-Chlor-2-hydroxyacetophenon 5-Chlor-2-hydroxyacetophenon 3,5-Dichlor-2-hydroxyacetophenon 3-Methyl-5-chlor-2-hydroxyacetophenon 2,4-Dihydroxyacetophenon 2,5-Dihydroxyacetophenon 2,6-Dihydroxyacetophenon 2,3-Dihydroxyacetophenon 2,4,6-Trihydroxyacetophenon 4-Pentyl-2,6-dihydroxyacetophenon 4-Heptyl-2,6-dihydroxyacetophenon 4-(1',1'-Dimethylpentyl)-2,6-dihydroxyacetophenon 3,4-Dimethoxy-6-methyl-2-hydroxyacetophenon 3,4,6-Trimethyl-2-hydroxyacetophenon 3-Methoxy-2-hydroxyacetophenon 4-Methoxy-2-hydroxyacetophenon 5-Methoxy-2-hydroxyacetophenon 6-Methoxy-2-hydroxyacetophenon 4-Benzyloxy-2-hydroxyacetophenon 5-Benzyloxy-2-hydroxyacetophenon 4-Phenoxy-2-hydroxyacetophenon 4-Cyclohexyl-2-hydroxyacetophenon 5-Phenyl-2-hydroxyacetophenon 3-β-Phenyläthyl-2-hydroxyacetophenon 5- -Phenylbutyl-2-hydroxyacetophenon 3,5-Dibrom-2-hydroxyacetophenon 4-Äthoxy-2-hydroxyacetophenon 5-Äthoxycarbonyl-äthoxy-2-hydroxyacetophenon 4-Methoxycarbonylmethoxy-2-hydroxyacetophenon 4-Carboxymethyl-2-hydroxyacetophenon 5-Nitro-2-hydroxyacetophenon 3-Cyan-2-hydroxyacetophenon 4-Trifluormethyl-2-hydroxyacetophenon 5-Trifluormethyl-2-hydroxyacetophenon 3-Trifluormethyl-2-hydroxyacetophenon 3-Methoxycarbonyl-2-hydroxyacetophenon 5-Carboxy-2-hydroxyacetophenon 5-Dimethylamino-2-hydroxyacetophenon 4-N-Piperidinyl-2-hydroxyacetophenon 3-rhenoxy-2-hydroxyacetophenon 4-p-Chlorphenoxy-2-hydroxyacetophenon 5-p-Tolyl-2-hydroxyacetophenon 1-Hydroxy-2-acetylnaphthalin 2-Hydroxy-1-acetylnaphthalin
The o-hydroxy-aryl-carbonyl compounds which can be used for the process according to the invention are known (cf. Beilstein, Handbuch der Organischen Chemie, H8, page 85 ff.). For example called:
  • o-Hydroxyacetophenone 3-chloro-2-hydroxyacetophenone 5-chloro-2-hydroxyacetophenone 3,5-dichloro-2-hydroxyacetophenone 3-methyl-5-chloro-2-hydroxyacetophenone 2,4-dihydroxyacetophenone 2,5-dihydroxyacetophenone 2.6 -Dihydroxyacetophenone 2,3-dihydroxyacetophenone 2,4,6-trihydroxyacetophenone 4-pentyl-2,6-dihydroxyacetophenone 4-heptyl-2,6-dihydroxyacetophenone 4- (1 ', 1'-dimethylpentyl) -2,6-dihydroxyacetophenone 3 , 4-Dimethoxy-6-methyl-2-hydroxyacetophenone 3,4,6-trimethyl-2-hydroxyacetophenone 3-methoxy-2-hydroxyacetophenone 4-methoxy-2-hydroxyacetophenone 5-methoxy-2-hydroxyacetophenone 6-methoxy-2- hydroxyacetophenone 4-benzyloxy-2-hydroxyacetophenone 5-benzyloxy-2-hydroxyacetophenone 4-phenoxy-2-hydroxyacetophenone 4-cyclohexyl-2-hydroxyacetophenone 5-phenyl-2-hydroxyacetophenone 3-β-phenylethyl-2-hydroxyacetophenone 5- -phenylbutyl-2-hydroxyacetophenone 3,5-dibromo-2-hydroxyacetophenone 4-ethoxy-2-hydroxyacetophenone 5-ethoxycarbonyl-ethoxy-2-hydroxyacetophenone 4-methoxycarbonylmethoxy-2-hydroxyacetophenone -Carboxymethyl-2-hydroxyacetophenone 5-nitro-2-hydroxyacetophenone 3-cyano-2-hydroxyacetophenone 4-trifluoromethyl-2-hydroxyacetophenone 5-trifluoromethyl-2-hydroxyacetophenone 3-trifluoromethyl-2-hydroxyacetophenone 3-methoxyacetophenone 5-methoxycarbonylophenone Carboxy-2-hydroxyacetophenone 5-dimethylamino-2-hydroxyacetophenone 4-N-piperidinyl-2-hydroxyacetophenone 3-rhenoxy-2-hydroxyacetophenone 4-p-chlorophenoxy-2-hydroxyacetophenone 5-p-tolyl-2-hydroxyacetophenone 1-hydroxy- 2-acetylnaphthalene 2-hydroxy-1-acetylnaphthalene

Weiterhin werden als Ausgangsverbindungen noch die Glyoxylsäure-Derivate der Formel (III) benötigt. In der Formel (III) steht Z bevorzugt für ein- oder zweiwertige Kationen von Alkali- und Erdalkali-Metallen, sowie für das AmmoniumKation und die Mono-, Di- und Trialkylamnonium-Kationen. In den drei letztgenannten Fällen enthalten die Alkylreste vorzugsweise bis zu 2 Kohlenstoffatome.The glyoxylic acid derivatives of the formula (III) are also required as starting compounds. In the formula (III) Z is preferably monovalent or divalent cations of alkali and alkaline earth metals, and ONO for the ammonium cation and M, di- and Trialkylamnonium cations. In the latter three cases, the alkyl radicals preferably contain up to 2 carbon atoms.

Die Synthese wird in Gegenwart von basischen Verbindungen durchgeführt. Als solche kommen bevorzugt sekundäre Amine in Frage, insbesondere cyclische Amine wie Pyrrolidin, ferner Piperidin, N-Methyl-piperazin, Morpholin, aber auch offenkettige Amine wie Dimethylamin und Diäthylamin. Die genannten Verbindungen sind allgemein bekannt.The synthesis is carried out in the presence of basic compounds. Secondary amines are preferred as such, in particular cyclic amines such as pyrrolidine, also piperidine, N-methylpiperazine, morpholine, but also open-chain amines such as dimethylamine and diethylamine. The compounds mentioned are generally known.

Das erfindungsgemäße Verfahren kann mit oder ohne Lösungsmittel durchgeführt werden. Zur Durchführung des Verfahrens kommen alle Lösungsmittel in Betracht, die gegenüber den Ausgangskomponenten und dem Endprodukt inert sind. Als Lösungsmittel seien beispielsweise genannt:

  • Aliphatische oder aromatische Kohlenwasserstoffe, wie Petroläther, Benzol, Toluol oder Xylol, aliphatische oder aromatische Halogenkohlenwasserstoffe, wie Tetrachlorkohlenstoff, Chlorbenzol oder Dichlorbenzol, Äther, wie Diäthyläther, Tetrahydrofuran, Dioxan oder Glykoldimethyläther, sodann Amide, wie Dimethylformamid, Dimethylacetamid und N-Methylpyrrolidon, ferner Ester wie Essigsäureäthylester, Nitrile, wie Acetonitril, Propionnitril, und Alkohole, wie Methanol, Äthanol und Glykolmonomethyläther, und schließlich Wasser.
The process according to the invention can be carried out with or without a solvent. All solvents which are inert to the starting components and the end product can be used to carry out the process. Examples of solvents are:
  • Aliphatic or aromatic hydrocarbons, such as petroleum ether, benzene, toluene or xylene, aliphatic or aromatic halohydrocarbons such as carbon tetrachloride, chlorobenzene or dichlorobenzene, ethers such as diethyl ether, tetrahydrofuran, dioxane or Glykoldimethyläther, then amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and Esters such as ethyl acetate, nitriles such as acetonitrile, propionitrile, and alcohols such as methanol, ethanol and glycol monomethyl ether, and finally water.

Das erfindungsgemäße Verfahren kann bei einer Temperatur von -30 bis +150°C, bevorzugt von 20 bis 80oC, durchgeführt werden.The inventive process may at a temperature of -30 to + 150 ° C, preferably from 20 to 80 o C, to be performed.

Zur Durchführung des erfindungsgemäßen Verfahrens werden im allgemeinen die o-Hydroxycarbonyl-Verbindungen und das Salz der Glyoxylsäure in stöchiometrischen Mengen, also im Verhältnis 1:2, eingesetzt. Für die Durchführung des erfindungsgemäßen Verfahrens ist es jedoch ohne Bedeutung, wenn ein kleiner Überschuß einer Komponente, insbesondere des Glyoxylsäuresalzes, eingesetzt wird (z.B. bis zum Molverhältnis 1:2,5). Die Menge des eingesetzten Amins ist nicht kritisch. Im allgemeinen verwendet man 0,05 bis 1,5, bevorzugt 0,1 bis 1 Mol des Amins, bezogen auf 1 Mol der o-Hydroxycarbonyl-Verbindung. Falls die o-Hydroxyacetophenone durch sauer reagierende Gruppen wie z.B. Carboxygruppen, substituiert sind, kann es zweckmäßig sein, durch einen Uberschuß des Amins die sauren Gruppen zu neutralisieren.To carry out the process according to the invention, the o-hydroxycarbonyl compounds and the salt of glyoxylic acid in stoichiometric amounts, ie in a ratio of 1: 2. For the implementation of the process according to the invention, however, it is of no importance if a small excess of a component, in particular the glyoxylic acid salt, is used (for example up to a molar ratio of 1: 2.5). The amount of the amine used is not critical. In general, 0.05 to 1.5, preferably 0.1 to 1 mol of the amine, based on 1 mol of the o-hydroxycarbonyl compound, is used. If the o-hydroxyacetophenones are substituted by acidic groups such as carboxy groups, it may be expedient to neutralize the acidic groups with an excess of the amine.

Im allgemeinen wird das erfindungsgemäße Verfahren wie folgt ausgeführt:

  • Die Ausgangsverbindungen werden bei der gewählten Reaktionstemperatur, gegebenenfalls in einem Lösungsmittel, gelöst und mit dem Amin versetzt. Durch die exotherme Reaktion steigt die Reaktionstemperatur im allgemeinen an, so daß eine weitere Erwärmung nicht notwendig ist. Man läßt dann das Reaktionsgemisch bis zur Beendigung der Reaktion ohne weitere Erwärmung stehen, kann jedoch auch die Reaktionszeit durch äußeres Erwärmen abkürzen. Nach Beendigung der Reaktion isoliert man die Chromon-Derivate, indem man die entstandenen Salze in Wasser löst und diese Lösungen ansäuert, beispielsweise mit Mineralsäuren wie Salz-, Schwefel- oder Phosphorsäure. Man erhält dann die Dicarbonsäure-Verbindungen der Formel (I), wobei R3 für Wasserstoff steht.
In general, the process according to the invention is carried out as follows:
  • The starting compounds are dissolved at the selected reaction temperature, if appropriate in a solvent, and the amine is added. The reaction temperature generally rises due to the exothermic reaction, so that further heating is not necessary. The reaction mixture is then left to stand without further heating until the reaction has ended, but the reaction time can also be shortened by external heating. After the reaction has ended, the chromone derivatives are isolated by dissolving the salts formed in water and acidifying these solutions, for example using mineral acids such as hydrochloric, sulfuric or phosphoric acid. The dicarboxylic acid compounds of the formula (I) are then obtained, where R 3 is hydrogen.

Die Veresterung der erhaltenen Dicarbonsäuren kann beispielsweise in üblicher Weise dadurch erfolgen, daß man die Dicarbonsäure in der 4- bis 100-, vorzugsweise 10- bis 50-fachen molaren Menge Alkohol der Formel R3-OH verrührt, mit einer Säure wie konz. Schwefelsäure versetzt oder mit Chlorwasserstoff-Gas sättigt und einige Stunden auf Temperaturen von 60 bis 120°C erwärmt. Man kann das Gemisch der Dicarbonsäure mit dem Alkohol auch mit der mindestens doppelten molaren Menge, bezogen auf die Dicarbonsäure, eines Dehydratisierungsmittels, wie anorganischen Säurehalogeniden, z.B. Thionylchlorid oder Phosphoroxychlorid, versetzen. Schließlich kann man auch Salze der Dicarbonsäuren mit mindestens der doppelten molaren Menge eines Alkylhalogenids in einem Lösungsmittel wie Dimethylsulfoxid oder Dimethylformamid zur Reaktion bringen.The esterification of the dicarboxylic acids obtained can be carried out, for example, in a customary manner by stirring the dicarboxylic acid in 4 to 100, preferably 10 to 50 times the molar amount of alcohol of the formula R 3 --OH, with an acid such as conc. Added sulfuric acid or saturated with hydrogen chloride gas and warmed to temperatures from 60 to 120 ° C for a few hours. The mixture of the dicarboxylic acid with the alcohol can also be mixed with at least twice the molar amount, based on the dicarboxylic acid, of a dehydrating agent, such as inorganic acid halides, for example thionyl chloride or phosphorus oxychloride. Finally, salts of the dicarboxylic acids can also be reacted with at least twice the molar amount of an alkyl halide in a solvent such as dimethyl sulfoxide or dimethylformamide.

Als neue Chromondicarbonsäuren und deren Ester seien beispielsweise genannt:

  • 2-Carboxy-3-carboxymethyl-6-chlor-chromon 2-Carboxy-3-carboxymethyl-7-chlor-chromon 2-Carboxy-3-carboxymethyl-8-chlor-chromon 2-Carboxy-3-carboxymethyl-6,8-dichlor-chromon 2-Carboxy-3-carboxymethyl-6-methyl-chromon 2-Carboxy-3-carboxymethyl-7-methyl-chromon 2-Carboxy-3-carboxymethyl-6-isobutyl-chromon 2-Carboxy-3-carboxymethyl-7-äthyl-chromon 2-Carboxy-3-carboxymethyl-6-sek.-butyl-chromon 2-Carboxy-3-carboxymethyl-6-benzyl-chromon 2-Carboxy-3-carboxymethyl-7-phenyl-chromon 2-Carboxy-3-carboxymethyl-5-methoxy-chromon 2-Carboxy-3-carboxymethyl-6-methoxy-chromon 2-Carboxy-3-carboxymethyl-7-methoxy-chromon 2-Carboxy-3-carboxymethyl-8-methoxy-chromon 2-Carboxy-3-carboxymethyl-6-chlor-8-methyl-chromon 2-Carboxy-3-carboxymethyl-6-pyrrolidinyl-chromon 2-Carboxy-3-carboxymethyl-6-dimethylamino-chromon 2-Carboxy-3-carboxymethyl-7,8-dimethoxy-chromon 2-Carboxy-3-carboxymethyl-6,7-dimethoxy-chromon 2-Carboxy-3-carboxymethyl-6-methoxycarbonyl-chromon 2-Carboxy-3-carboxymethyl-8-carboxy-chromon 2-Carboxy-3-carboxymethyl-7-cyan-chromon 2-Carboxy-3-carboxymethyl-6-cyan-chromon 2-Carboxy-3-carboxymethyl-5,6,7-trimethyl-chromon 2-Carboxy-3-carboxymethyl-5,6-benzo-chromon 2-Carboxy-3-carboxymethyl-5,6-trimethylen-chromon 2-Carboxy-3-carboxymethyl-5-methyl-6,8-dichlor-chromon 2-Carbomethoxy-3-carbomethoxymethyl-6-chlor-chromon 2-Carbomethoxy-3-carbomethoxymethyl-7-chlor-chromon 2-Carbomethoxy-3-carbomethoxymethyl-6,8-dichlor-chromon 2-Carbomethoxy-3-carbomethoxymethyl-6-methyl-chromon 2-Carbomethoxy-3-carbomethoxymethyl-7-methyl-chromon 2-Carbomethoxy-3-carbomethoxymethyl-6-isobutyl-chromon 2-Carbomethoxy-3-carbomethoxymethyl-6-cyclopentyl-chromon 2-Carbanethoxy-3-carbomethoxymethyl-7-phenyl-chromon 2-Carbomethoxy-3-carbomethoxymethyl-S-methoxy-chramon 2-Carbomethoxy-3-carbomethoxymethyl-6-methoxy-chromon 2-Carboenethoxy-3-carbomethoxymethyl-7-methoxy-chromon 2-Carbomethoxy-3-carbomethoxymethyl-8-methoxy-chrason 2-Carbomethoxy-3-carbomethoxymethyl-6-chlor-8-methyl-chromon 2-Carbomethoxy-3-carbomethoxymethyl-7,8-dimethoxy-chromon 2-Carbomethoxy-3-carbomethoxymethyl-6,7-dimethoxy-chromon 2-Carbomethoxy-3-carbomethoxymethyl-8-carboxy-chromon 2-Carbomethoxy-3-carbomethoxymethyl-6-cyan-chromon 2-Carbomethoxy-3-carbomethoxymethyl-5,6-benzo-chromon 2-Carbomethoxy-3-carbomethoxymethyl-5-methyl-6,8-dichlor-chromon 2-Carbo-äthoxy-3-carbo-äthoxy methylchromon 2-Carbo-propoxy-3-carbo-propoxy methylchromon 2-Carbo-isopropoxy-3-carbo-isopropoxy methylchromon 2-Carbo-butoxy-3-carbo-butoxy methylchromon 2-Carbo-sek.-butoxy-3-carbo-sek. butoxy methylchromon 2-Carbo-iso-butoxy-3-carbo-iso-butoxy methylchromon 2-Carbo-tert.-butoxy-3-carbo-tert.-butoxy methylchromon 2-Carbo-benzyloxy-3-carbo-benzyloxy methylchromon 2-Carbo-phenäthoxy-3-carbo-phenäthoxy methylchromon 2-Carbo-cyclopentyloxy-3-carbo-cyclopentyloxy methylchromon 2-Carbo-cyclohexyloxy-3-carbo-cyclohexyloxy methylchromon 2-Carbo-allyloxy-3-carbo-allyloxy methylchromon 2-Carbo-p-chlorbenzyloxy-3-carbo-p-Chlorbenzyloxy methylchromon 2-Carbo-2'-methoxyäthoxy-3-carbo-2'-methoxyäthoxy methylchromon 2-Carbo-2'-bromäthoxy-3-carbo-2'-bromätboxy methylchromon
Examples of new chromondicarboxylic acids and their esters are:
  • 2-carboxy-3-carboxymethyl-6-chloro-chromon 2-carboxy-3-carboxymethyl-7-chloro-chromon 2-carboxy-3-carboxymethyl-8-chloro-chromon 2-carboxy-3-carboxymethyl-6.8 -dichloro-chromon 2-carboxy-3-carboxymethyl-6-methyl-chromon 2-carboxy-3-carboxymethyl-7-methyl-chromon 2-carboxy-3-carboxymethyl-6-isobutyl-chromon 2-carboxy-3-carboxymethyl -7-ethyl-chromon 2-carboxy-3-carboxymethyl-6-sec-butyl-chromon 2-carboxy-3-carboxymethyl-6-benzyl-chromon 2-carboxy-3-carboxymethyl-7-phenyl-chromon 2-carboxy-3-carboxymethyl-5-methoxy-chromon 2-carboxy-3-carboxymethyl-6-methoxy-chromon 2-carboxy-3-carboxymethyl-7-methoxy-chromon 2-carboxy-3-carboxymethyl-8-methoxy -chromon 2-carboxy-3-carboxymethyl-6-chloro-8-methyl-chromon 2-carboxy-3-carboxymethyl-6-pyrrolidinyl-chromon 2-carboxy-3-carboxymethyl-6-dimethylamino-chromon 2-carboxy-3 -carboxymethyl-7,8-dimethoxy-chromon 2-carboxy-3-carboxymethyl-6,7-dimethoxy-chromon 2-carboxy-3-carboxymethyl-6-methoxycarbonyl-chromon 2-carboxy-3-carboxymethyl-8-carboxy- chromon 2-carboxy-3-carboxymethyl-7-cyan-chromon 2-carboxy-3-carboxymethyl-6-cyan-chromon 2-carboxy-3-carboxymethyl-5,6,7-trimethyl-chromon 2-carboxy-3- carboxymethyl-5,6-benzo-chromon 2-carboxy-3-carboxymethyl-5,6-trimethylene-chromon 2-carboxy-3-carboxymethyl-5-methyl-6,8-dichloro-chromon 2-carbomethoxy-3-carbomethoxymethyl -6-chloro-chromon 2-carbomethoxy-3-carbomethoxymethyl-7-chloro-chromon 2-carbomethoxy-3-carbomethoxymethyl-6,8-dichloro-chromon 2-carbomethoxy-3-carbomethoxymethyl-6-met hyl-chromon 2-carbomethoxy-3-carbomethoxymethyl-7-methyl-chromon 2-carbomethoxy-3-carbomethoxymethyl-6-isobutyl-chromon 2-carbomethoxy-3-carbomethoxymethyl-6-cyclopentyl-chromon 2-carbanethoxy-3-carbomethoxymethyl- 7-phenyl-chromon 2-carbomethoxy-3-carbomethoxymethyl-S-methoxy-chramon 2-carbomethoxy-3-carbomethoxymethyl-6-methoxy-chromon 2-carboenethoxy-3-carbomethoxymethyl-7-methoxy-chromon 2-carbomethoxy-3- carbomethoxymethyl-8-methoxy-chrasone 2-carbomethoxy-3-carbomethoxymethyl-6-chloro-8-methyl-chromon 2-carbomethoxy-3-carbomethoxymethyl-7,8-dimethoxy-chromon 2-carbomethoxy-3-carbomethoxymethyl-6,7-dimethoxy-chromon 2-carbomethoxy -3-carbomethoxymethyl-8-carboxy-chromon 2-carbomethoxy-3-carbomethoxymethyl-6-cyan-chromon 2-carbomethoxy-3-carbomethoxymethyl-5,6-benzo-chromon 2-carbomethoxy-3-carbomethoxymethyl-5-methyl- 6,8-dichloro-chromon 2-carbo-ethoxy-3-carbo-ethoxy methylchromone 2-carbo-propoxy-3-carbo-propoxy methylchromone 2-carbo-isopropoxy-3-carbo-isopropoxy methylchromone 2-carbo-butoxy-3 -carbo-butoxy methylchromon 2-carbo-sec.-butoxy-3-carbo-sec. butoxy methylchromone 2-carbo-iso-butoxy-3-carbo-iso-butoxy methylchromone 2-carbo-tert-butoxy-3-carbo-tert-butoxy methylchromone 2-carbo-benzyloxy-3-carbo-benzyloxy methylchromone 2- Carbo-phenethoxy-3-carbo-phenethoxy methylchromon 2-carbo-cyclopentyloxy-3-carbo-cyclopentyloxy methylchromon 2-carbo-cyclohexyloxy-3-carbo-cyclohexyloxy methylchromon 2-carbo-allyloxy-3-carbo-allyloxy methylchromon 2-carbo p-chlorobenzyloxy-3-carbo-p-chlorobenzyloxy methylchromone 2-carbo-2'-methoxyethoxy-3-carbo-2'-methoxyethoxy methylchromone 2-carbo-2'-bromoethoxy-3-carbo-2'-bromoetboxy methylchromone

Die erfindungsgemäßen Wirkstoffe weisen eine gute fungitoxische Wirkung auf. Sie schädigen Kulturpflanzen in den zur Bekämpfung von Pilzen notwendigen Konzentrationen nicht. Aus diesen Gründen sind sie für den Gebrauch als Pflanzenschutzmittel zur Bekämpfung von Pilzen geeignet. Fungitoxische Mittel im Pflanzenschutz werden eingesetzt zur Bekämpfung von Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Bsidiomycetes, Deuteromycetes.The active compounds according to the invention have a good fungitoxic effect. They do not damage crops in the concentrations necessary to control fungi. For these reasons, they are suitable for use as crop protection agents for combating fungi. Fungitoxic agents are used in crop protection to combat Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Bsidiomycetes, Deuteromycetes.

Die erfindungsgemäßen Wirkstoffe können angewandt werden gegen parasitäre Pilze und Bakterien, die oberirdische Pflanzenteile befallen oder die Pflanzen vom Boden her angreifen, sowie gegen samenübertragbare Krankheitserreger.The active compounds according to the invention can be used against parasitic fungi and bacteria which attack above-ground parts of plants or attack the plants from the ground, and against seed-borne pathogens.

Die gute Pflanzenverträglichkeit erlaubt eine Anwendung gegen pilzliche Pflanzenkrankheiten durch Behandlung der stehenden Kulturpflanze oder einzelner Teile von ihr oder des Saatgutes oder auch des Kulturbodens. Die Wirk-. stoffe sind besonders Wirksam gegen Getreidemehltau.The good tolerance to plants allows use against fungal plant diseases by treating the standing crop or individual parts of it or the seed or the crop soil. The active. substances are particularly effective against powdery mildew.

Die erfindungsgemäßen Wirkstoffe können in die Üblichen Formulierungen übergeführt werden, wie Lösungen, Emulsionen, Suspensionen, Pulver, Pasten und Granulate. Diese werden in bekannter Weise hergestellt, z. B. durch Vermischen der Wirkstoffe mit Streckmitteln, also flüssigen Lösungsmitteln, unter Druck stehenden verflüssigten Gasen und/oder festen Trägerstoffen, gegebenenfalls unter Verwendung von oberflächenaktiven Mitteln, also Emulgiermitteln und/oder Dispergiermitteln und/oder schaumerzeugenden Mitteln. Im Falle der Benutzung von Wasser als Streckmittel können z. B. auch organische Lösuncsmittel als Hilfslösungsmittel verwendet werden. Als flüssige Lösungsmittel kommen im wesentlichen in Frage: Aromaten, wie Xylol, Toluol, Benzol oder Alkylnaphthaline, chlorierte Arossten oder chlorierte aliphatische Kohlenwasserstoffe, wie Chlorbenzole, Chloräthylene oder Methylenchlorid, aliphatische Kohlenwasserstoffe, wie Cyclohexan oder Paraffine, z. B. Erdölfraktionen, Alkohole, wie Butanol oder Glycol sowie deren Äther und Ester, Ketone, wie Aceton, Methyläthylketon, Methylisobutylketon oder Cyclohexanon, stark polare Lösungsmittel, wie Dimethylformamid und Dimethylsulfoxid, sowie Wasser; mit verflüssigten gasförmigen Streckmitteln oder Trägerstoffen sind solche Flüssigkeiten gemeint, welche bei normaler Temperatur und unter Normaldruck gasförmig sind, z. B. Aerosol-Treibgase, wie Dichlordifluormethan oder Trichlorfluormethan; als feste Trägerstoffe: naturliche Gesteinsmehle, wie Kaoline, Tonerden, Talkum, Kreide, Quarz, Attapulgit, Montmorillonit oder Diatomeenerde und synthetische Gesteinsmehle, wie hochdisperse Kieselsäure, Aluminiumoxid und Silikate; als Emulgiermittel; nichtionogene und anionische Emulgatoren, wie Polyoxyäthylen-Fottsäure-Ester,Polyoxy- äthylen-Fettalkohol-Äther, z.B. Alkylaryl-polyglycol-Äther, Alkylsulfonate, Alkylsulfate, Arylsulfonate sowie Eiweißhydrolysate; als Dispergiermittel: z. B. Lignin-Sulfitablaugen und Methylcellulose.The active compounds according to the invention can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, pastes and granules. These are manufactured in a known manner, e.g. B. by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. In the case of the use of water as an extender, e.g. B. organic solvents can also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, benzene or alkylnaphthalenes, chlorinated aroses or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, Chloroethylene or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. B. petroleum fractions, alcohols, such as butanol or glycol and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water; Liquefied gaseous extenders or carriers mean those liquids which are gaseous at normal temperature and pressure, e.g. B. aerosol propellants such as dichlorodifluoromethane or trichlorofluoromethane; as solid carriers: natural rock flour, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock meals, such as highly disperse silica, aluminum oxide and silicates; as an emulsifier; nonionic and anionic emulsifiers, such as polyoxyethylene photo acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ether, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; as a dispersant: e.g. B. lignin sulfite and methyl cellulose.

Die Formulierungen enthalten im allgemeinen zwischen 0,1 und 95 Gewichtsprozent Wirkstoff, vorzugsweise zwischen O,5 und 90 %.The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.

Die Wirkstoffe können als solche, in Form ihrer Formulierungen oder der daraus bereiteten Anwendungsformen, wie gebrauchsfertige Lösungen, Emulsionen, Suspensionen, Pulver, Pasten und Granulate angewendet werden. Die Anwendung geschieht in üblicher Weise, z.B. durch Spritzen, Sprühen, Nebeln, Streuen, Stäuben, Gießen, Trockenbeizen, Schlämmbeizen (Slurrybeizen), Feuchtbeizen und Naßbeizen.The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. They are used in the usual way, e.g. by spraying, spraying, misting, scattering, dusting, pouring, dry pickling, slurry pickling (slurry pickling), wet pickling and wet pickling.

Der Wirkstoffgehalt der aus den handelsüblichen Formulierungen bereiteten Anwendungsformen kann in weiten Bereichen variieren. Die Wirkstoffkonzentration der Anwendungsformen kann von 0,0000001 bis zu 100 Gew.-% Wirkstoff, vorzugsweise zwischen 0,01 und 10 Gew.-% liegen.The active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges. The active substance concentration of the use forms can be from 0.0000001 to 100% by weight of active substance, preferably between 0.01 and 10% by weight.

Bei der Beizung kommen im allgemeinen je Kilogramm Saatgut Wirkstoffmengen von 10 mg bis 10 g, vorzugsweise 100 mg bis 3 q zur Anwendung. Bei der Bodenhandlung, die ganzflächig, streifenförmig oder punktförmig durchgeführt werden kann, werden am Ort der erwarteten Wirkung Wirkstoffkonzentrationen von 1 bis 1000 g Wirkstoff je m3 Boden benötigt, vorzugsweise 10 bis 200 g pro m3.In the case of dressing, amounts of active compound of 10 mg to 10 g, preferably 100 mg to 3 q, are generally used per kilogram of seed. In the soil handling, which can be carried out over the whole area, in strips or in punctiform form, active substance concentrations of 1 to 1000 g of active substance per m 3 of soil, preferably 10 to 200 g per m 3 , are required at the location of the expected action.

Wie schon erwähnt, hemmen die erfindungsgemäßen Verbindungen die Entwicklung von Gliederfüßlern (Arthrophoden).As already mentioned, the compounds according to the invention inhibit the development of arthropods (arthrophodes).

Durch den im folgenden angegebenen Versuche wird die arthropodenmethamorphosehemmende Wirkung der erfindungsgemäßen Verbindungen gezeigt, ohne eine Beschränkung hinsichtlich der Wirkungsbreite dieser Verbindungen vornehmen zu wollen. Dabei werden während der gesamten angegebenen Entwicklung der Testtiere die morphologischen Veränderungen, wie zur Hälfte verpuppte Tiere, unvollständig geschlüpfte Larven oder Raupen, defekte Flügel, puppale Kutikula bei Imagines sowie das Absterben bewertet. Die Summe der morphologischen Mißbildungen und der Abtötung während der Entwicklung werden bonitiert.The tests given below show the arthropod methamorphosis-inhibiting activity of the compounds according to the invention, without wishing to carry out any restriction with regard to the range of action of these compounds. During the entire development of the test animals, the morphological changes, such as half pupated animals, incompletely hatched larvae or caterpillars, defective wings, puppal cuticles in adults as well as the death are assessed. The sum of the morphological M ißbildungen and killing during development are scored.

Beispiel AExample A

Entwicklungshemmende Wirkung / Fraßtest Testtiere: Plutella maculipennis (Raupen im 4. Entwicklungsstadium) 20 Stück Phaedon cochleariae (Larven im 4. Entwicklungsstadium) 20 Stück Futterpflanzen: Kohlpflanzen (Brasica oleracea) Lösungsmittel: 4 Gew.-Teile Aceton Emulgator: 1 Gew.-Teil AlkylarylpolyglykolätherDevelopmental inhibiting effect / feeding test Test animals: Plutella maculipennis (caterpillars in the 4th stage of development) 20 pieces of Phaedon cochleariae (larvae in the 4th stage of development) 20 pieces of fodder plants: Cabbage plants (Brasica oleracea) Solvent: 4 parts by weight of acetone emulsifier: 1 part by weight Alkylaryl polyglycol ether

Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 2 Gewichtsteile Wirkstoff mit der angegebenen Menge Lösungsmittel, Emulgator und soviel Wasser, daß eine 1 %ige Mischung entsteht, die mit Wasser auf die gewünschte Konzentration verdünnt wird.To produce a suitable preparation of active compound, 2 parts by weight of active compound are mixed with the stated amount of solvent, emulsifier and enough water to form a 1% mixture which is diluted with water to the desired concentration.

Die Testtiere werden mit Blättern der Futterpflanzen, die mit einem gleichmäßigen Spritzbelag der Wirkstoffmischung der gewählten Konzentration versehen sind, so daß eine Wirkstoffmenge in ppm ("parts pro million") auf den Blättern erhalten wird, bis zur Entwicklung der Imago gefüttert.The test animals are such that an amount of active ingredient is obtained in ppm ( "parts p ro million") on the leaves, fed with leaves of the feed plants, which are provided with a uniform spray coating of the active ingredient mixture of the chosen concentration, to the development of the imago.

Zur Kontrolle werden nur mit Lösungsmittel und Emulgator der angegebenen Konzentration versehene Blätter verfüttert.As a control, only leaves provided with solvent and emulsifier of the specified concentration are fed.

Die Versuchsauswertung ergab, daß insbesondere die folgenden erfindungsgemäßen Verbindungen einem bekannten Vergleichspräparat (2,2-Dimethyl-6-methoxy-benzopyran) überlegen sind:

  • Verbindungen gemäß Herstellungsbeispielen 3, 5 und 10.
The evaluation of the experiment showed that the following compounds according to the invention in particular are superior to a known comparative preparation (2,2-dimethyl-6-methoxy-benzopyran):
  • Compounds according to Preparation Examples 3, 5 and 10.

Beispiel BExample B

Sproßbehandlunqs-Test / Getreidemehltau / protektiv (blattzerstörende Mykose)Shoot treatment test / powdery mildew / protective (leaf-destroying mycosis)

Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung nimmt man 0,25 Gewichtsteile Wirkstoff in 25 Gewichtsteilen Dimethylformamid und 0,06 Gewichtsteilen Emulgator (Alkyl-aryl-polyglkyoläther) auf und gibt 975 Gewichtsteile Wasser hinzu. Das Konzentrat verdünnt man mit Waser auf die gewünschte Endkonzentration der Spritzbrühe.To prepare a suitable preparation of active compound, 0.25 part by weight of active compound is taken up in 25 parts by weight of dimethylformamide and 0.06 part by weight of emulsifier (alkyl aryl polyglycol ether), and 975 parts by weight of water are added. The concentrate is diluted with water to the desired final concentration of the spray mixture.

Zur Prüfung auf protektive Wirksamkeit besprüht man die einblättrigen Gerstenjungpflanzen der Sorte Amsel mit der Wirkstoffzubereitung taufeucht. Nach Antrocknen bestäubt man die Gerstenpflanzen mit Sporen von Erysiphe graminis var. hordei.To test for protective activity, the single-leafed barley young plants of the Amsel variety are sprayed with the preparation of active compound as dewy. After drying, the barley plants are dusted with spores from Erysiphe graminis var. Hordei.

Nach 6 Tagen Verweilzeit der Pflanzen bei einer Temperatur von 21 bis 22°C und einer Luftfeuchtigkeit von 80 bis 90 % wertet man den Besatz der Pflanzen mit Mehltaupusteln aus. Der Befallsgrad wird in Prozenten des Befalls der unbehandelten Kontrollpflanzen ausgedrückt. Dabei bedeutet O % keinen Befall und 100 % den gleichen Befallsgrad wie bei der unbehandelten Kontrolle. Der Wirkstoff ist umso wirksamer, je geringer der Mehltaubefall ist.After 6 days of dwell time of the plants at a temperature of 21 to 22 ° C and a humidity of 80 to 90%, the stocking of the plants with mildew pustules is evaluated. The degree of infestation is expressed as a percentage of the infestation of the untreated control plants. O% means no infection and 100% means the same degree of infection as in the untreated control. The lower the mildew infestation, the more effective the active ingredient.

Wirkstoffe, Wirkstoffkonzentrationen in der Spritzbrühe .und Befallsgrade gehen aus der nachfolgenden Tabelle hervor:

Figure imgb0005
Active substances, active substance concentrations in the spray mixture and degrees of infestation are shown in the table below:
Figure imgb0005

Beispiel 1example 1

Figure imgb0006
75 g (0,55 m) o-Hydroxyacetophenon und 350 ml Wasser/Eis werden mit 60 ml Pyrrolidin verrührt. In die klare Lösung gibt man 250 g Natriumglyoxylat (Hydrat, ca. 50 %ig: 1,1 Mol) und rührt ohne Kühlung nach. Nach einigen Stunden ist das Salz fast klar gelöst; später scheidet sich ein Teil des Endproduktes als Di-Natrium-Salz ab. Nach 5 Tagen versetzt man mit ca. 600 ml Wasser, rührt nach, bis eine fast klare Lösung entsteht und versetzt das Filtrat mit konz. Salzsäure, bis ein pH-Wert von 1 erreicht ist. Der ausfallende Niederschlag wird nach 1 Tag abgesaugt und getrocknet. Ausbeute: 125 g 2-Carboxy-3-carboxymethyl-chromon vom Fp. 240 - 242°C, das sind 92 % der Theorie.
Figure imgb0006
 75 g (0.55 m) o-hydroxyacetophenone and 350 ml water / ice are stirred with 60 ml pyrrolidine. 250 g of sodium glyoxylate (hydrate, approx. 50%: 1.1 mol) are added to the clear solution and stirring is continued without cooling. After a few hours the salt is almost clear; later part of the end product separates out as disodium salt. After 5 days, 600 ml of water are added, the mixture is stirred until an almost clear solution is formed and the filtrate is mixed with conc. Hydrochloric acid until a pH of 1 is reached. The precipitate is filtered off after 1 day and dried. Yield: 125 g of 2-carboxy-3-carboxymethyl-chromon of mp 240-242 ° C, that's 92% of theory.

Beispiel 1 aExample 1 a

Man arbeitet wie in Beispiel 1 angegeben, erwärmt aber nach dem Zusammengeben der Ausgangstoffe während 30 Minuten auf 950C. Die Aufarbeitung ergibt 112 g 2-Carboxy-3-carboxymethyl-chromon, das sind 82 % der Theorie.The procedure is as indicated in example 1, but heated after mixing the starting materials for 30 minutes at 95 0 C. The work-up gives 112 g of 2-carboxy-3-carboxymethyl-chromone, which are 82% of theory.

Beispiel 2Example 2

Figure imgb0007
63 g 4-Phenyl-2-hydroxyacetophenon, 700 ml Isopropanol und 110 g einer 50 %igen Glyoxylsäure-Lösung in Wasser werden verrührt und bei einer Temperatur unterhalb von 0°C mit 63 g Pyrrolidin versetzt. Nach 6 Tagen wird die entstandene Lösung mit 1 Liter Wasser verdünnt und angesäuert. Ausbeute: 22 g 2-Carboxy-3-carboxymethyl-7-phenyl- chromon vom Fp. 219 - 221°C.
Figure imgb0007
 63 g of 4-phenyl-2-hydroxyacetophenone, 700 ml of isopropanol and 110 g of a 50% glyoxylic acid solution in water are stirred and 63 g of pyrrolidine are added at a temperature below 0.degree. After 6 days, the resulting solution is diluted with 1 liter of water and acidified. Yield: 22 g of 2-carboxy-3-carboxymethyl-7-phenyl-chromon, mp. 219-221 ° C.

Beispiel 3Example 3

(Veresterungs-Reaktion)

Figure imgb0008
Man verrührt 220 g 2-Carboxy-3-carboxymethyl-chromon (Herstellung gemäß Beispiel 1) in 2 Liter Methanol, leitet Chlorwasserstoff-Gas bis zur Sättigung ein und erwärmt gleichzeitig, bis die Rückflußtemperatur erreicht ist. Nach 8 Stunden läßt man abkühlen und saugt ab. Man erhält 196 g 2-Methoxycarbonyl-3-methoxycarbonylmethyl-chromon vom Fp 105°C.(Esterification reaction)
Figure imgb0008
 220 g of 2-carboxy-3-carboxymethyl-chromone (preparation according to Example 1) are stirred in 2 liters of methanol, hydrogen chloride gas is passed in until saturation is reached and the mixture is heated at the same time until the reflux temperature is reached. After 8 hours, the mixture is allowed to cool and is suctioned off. 196 g of 2-methoxycarbonyl-3-methoxycarbonylmethyl-chromon of mp 105 ° C. are obtained.

Beispiel 3 aExample 3 a (Veresterungs-Reaktion, vgl. Beispiel 3)(Esterification reaction, see Example 3)

Man verrührt 15 g 2-Carboxy-3-carboxymethyl-chromon in 60 ml Methanol und versetzt in ca. 10 Minuten mit 15 ml Thionylchlorid, wobei man die Temperatur unter 35°C hält. Anschließend heizt man während 2 Stunden auf 60°C, läßt abkühlen und saugt ab. Man erhält 13,5 g des gleichen Produktes wie in Beispiel 3 angegeben.15 g of 2-carboxy-3-carboxymethyl-chromone are stirred in 60 ml of methanol, and 15 ml are added in about 10 minutes Thionyl chloride, keeping the temperature below 35 ° C. The mixture is then heated to 60 ° C. for 2 hours, allowed to cool and suction filtered. 13.5 g of the same product as given in Example 3 are obtained.

Beispiel 4Example 4 (Veresterungs-Reaktion)(Esterification reaction)

Figure imgb0009
Man löst 25 g 2-Carboxy-3-carboxymethyl-chromon in 30 ml Dimethylsulfoxid und versetzt nacheinander mit 30 ml Triäthylamin und 30 g Benzylchlorid. Nach 24 Stunden gießt man auf Eiswasser, schüttelt mit Chloroform aus und wäscht die Chloroform-Schicht mit 100 ml 2n-Natronlauge und dann mit Wasser. Nach dem Trocknen und Einengen erhält man einen Rückstand, der aus Äther umkristallisiert wird. Die Ausbeute beträgt 17 g 2-Benzyloxycarbonyl-3-benzyloxycarbonylmethyl-chromon vom Fp. 82 - 84oC.
Figure imgb0009
 25 g of 2-carboxy-3-carboxymethyl-chromon are dissolved in 30 ml of dimethyl sulfoxide, and 30 ml of triethylamine and 30 g of benzyl chloride are added in succession. After 24 hours, the mixture is poured onto ice water, shaken out with chloroform and the chloroform layer is washed with 100 ml of 2N sodium hydroxide solution and then with water. After drying and concentrating, a residue is obtained which is recrystallized from ether. The yield is 17 g of 2-benzyloxycarbonyl-3-benzyloxycarbonylmethyl-chromon from F p. 82 - 84 o C.

In ähnlicher Weise wie in den Beispielen 1 bis 4 beschrieben, lassen sich die folgenden Verbindungen der allgemeinen Formel

Figure imgb0010
herstellen.
Figure imgb0011
 In a manner similar to that described in Examples 1 to 4, the following compounds of the general formula
Figure imgb0010
 produce.
Figure imgb0011

Claims (4)

1. Verfahren zur Herstellung von Chromon-Derivaten der allqemeinen Formel
Figure imgb0012
in welcher R, R1 und R2 gleich oder verschieden sein können und für Wasserstoff, gegebenenfalls substituiertes Alkyl, Alkenyl, Cycloalkyl, Cycloalkenyl, Aralkyl, Aryl, ferner für Halogen, Hydroxy, Alkoxy, Aryloxy, Aralkoxy, Alkoxycarbonyl, Cyan und/oder Dialkylamino stehen, und weiterhin zwei Reste R und R zusammen mit zwei Kohlenstoffatomen des Benzolringsystems einen carbocyclischen oder heterocyclischen 5- oder 6-Ring bilden können, und R 3 für Wasserstoff, gegebenenfalls substituiertes Alkyl, Alkenyl, Cycloalkyl, Cycloalkenyl oder Aralkyl steht, dadurch gekennzeichnet, daß man o-Hydroxyacetophenone der allgemeinen Formel
Figure imgb0013
in welcher R, R1 und R2 die oben angegebene Bedeutung haben, mit Glyoxylsäure-Derivaten der allgemeinen Formel
Figure imgb0014
in welcher Z für ein Kation steht, in Gegenwart von basischen Verbindungen umsetzt, und noch gegebenenfalls die dabei erhaltenen Carbonsäuren in an sich bekannter Weise in die entsprechenden Ester überführt. 1. Process for the preparation of chromone derivatives of the general formula
Figure imgb0012
 in which R , R 1 and R 2 may be the same or different and represent hydrogen, optionally substituted alkyl, alkenyl, cycloalkyl, cycloalkenyl, aralkyl, aryl, furthermore halogen, hydroxy, alkoxy, aryloxy, aralkoxy, alkoxycarbonyl, cyano and / or dialkylamino , and two remains R and R together with two carbon atoms of the benzene ring system can form a carbocyclic or heterocyclic 5- or 6-ring, and R 3 represents hydrogen, optionally substituted alkyl, alkenyl, cycloalkyl, cycloalkenyl or aralkyl, characterized in that o-hydroxyacetophenones of the general formula
Figure imgb0013
 in which R, R 1 and R 2 have the meaning given above, with glyoxylic acid derivatives of the general formula
Figure imgb0014
 in which Z represents a cation, in the presence of basic compounds, and optionally converting the carboxylic acids obtained in a manner known per se into the corresponding esters. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man als basische Verbindungen sekundäre Amine verwendet.2. The method according to claim 1, characterized in that secondary amines are used as basic compounds. 3. Verfahren nach Anspruch 1, dadurch gekennzeichnet; daß man die Umsetzung im Temperaturbereich zwischen -30 und +150°C durchführt.3. The method according to claim 1, characterized; that one carries out the reaction in the temperature range between -30 and + 150 ° C. 4. Verfahren nach Ansprüchen 1 und 3, dadurch gekennzeichnet, daß man die Umsetzung im Temperaturbereich zwischen +20 und 80°C durchführt.4. Process according to Claims 1 and 3, characterized in that the reaction is carried out in the temperature range between +20 and 80 ° C.
EP78100318A 1977-07-13 1978-07-06 Process for the preparation of chromone derivatives, new chromone derivatives and their use as plant-protecting agents Expired EP0000377B1 (en)

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EP0241003A2 (en) * 1986-04-11 1987-10-14 Hoechst Aktiengesellschaft 4H-1-benzopyran-4-one derivatives, process for their preparation and their use as medicaments
WO1998027080A1 (en) * 1996-12-19 1998-06-25 Agrevo Uk Limited Chromones useful as fungicides
US6812225B2 (en) 2001-01-16 2004-11-02 Astrazeneca Ab Therapeutic heterocyclic compounds
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JP4561245B2 (en) * 2004-08-31 2010-10-13 住友化学株式会社 Chromone compounds and uses thereof

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US3862143A (en) * 1972-12-04 1975-01-21 Warner Lambert Co Substituted chromone-3-carbonitriles, carboxamides and carboxylic acids

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JOURNAL OF THE CHEMICAL SOCIETY Perkin Transactions I (22) 1974, Seiten 2570-2574, Benzopyrones, Part XI Some 3-substituted 4-oxochromen-2-carboxilic acid derivates by Gwynn P. Ellis and Idris L. Thomas. *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0241003A2 (en) * 1986-04-11 1987-10-14 Hoechst Aktiengesellschaft 4H-1-benzopyran-4-one derivatives, process for their preparation and their use as medicaments
EP0241003A3 (en) * 1986-04-11 1988-10-12 Hoechst Aktiengesellschaft 4h-1-benzopyran-4-one derivatives, process for their preparation and their use as medicaments
WO1998027080A1 (en) * 1996-12-19 1998-06-25 Agrevo Uk Limited Chromones useful as fungicides
US6812225B2 (en) 2001-01-16 2004-11-02 Astrazeneca Ab Therapeutic heterocyclic compounds
US7026314B2 (en) 2001-01-16 2006-04-11 Astrazeneca Ab Therapeutic chromone compounds
US7045514B2 (en) 2001-01-16 2006-05-16 Astrazeneca Ab Therapeutic heterocyclic compounds
US7285662B2 (en) 2001-01-16 2007-10-23 Astrazeneca Ab Therapeutic heterocyclic compounds

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