EP0000377B1 - 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
EP0000377B1
EP0000377B1 EP78100318A EP78100318A EP0000377B1 EP 0000377 B1 EP0000377 B1 EP 0000377B1 EP 78100318 A EP78100318 A EP 78100318A EP 78100318 A EP78100318 A EP 78100318A EP 0000377 B1 EP0000377 B1 EP 0000377B1
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Prior art keywords
carbon atoms
chromon
alkyl
carboxy
carboxymethyl
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German (de)
French (fr)
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EP0000377A1 (en
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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 invention relates to a chemically unique process for the production of chromone derivatives, as well as 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)]
  • the new compounds of formula la have fungicidal properties; they also inhibit the development of arthropods. They are therefore of interest as pesticides.
  • R, R '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 with one or more double bonds and up to 8 Carbon atoms, preferably up to 3 carbon atoms and a double bond.
  • alkyl or alkenyl radicals are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, butene- (3) -yl and 4-methyl-penten- (3) -yl .
  • R, R 1 and R 2 furthermore 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.
  • R, R 1 and R 2 furthermore represent phenyl and naphthyl, preferably phenyl.
  • phenylalkyl and naphthylalkyl radicals are: benzyl, phenylethyl, phenylpropyl, phenylbutyl, naphthylmethyl and naphthylethyl, preferably benzyl.
  • alkoxy groups are those with up to 4 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy and tert-butoxy.
  • Preferred phenylalkoxy groups include benzyloxy, phenylethoxy, phenylpropoxy, phenylisopropoxy, phenylbutoxy, phenylisobutoxy and phenyl tert-butoxy.
  • Preferred alkoxycarbonyl groups are methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl.
  • Dimethylamino, diethylamino and diisopropylamino may be mentioned as preferred dialkylamino groups. 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 form a carbocyclic or heterocyclic five- or six-membered ring with the two carbon atoms of the benzene ring on which they are located, such as, for example, a cyclopentene, cyclohexene, benzene, furan, dihydrofuran, thiophene , 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 .
  • the halogens such as fluorine, chlorine, bromine and Called iodine and the cyano group, also the alkoxy and alkoxycarbonyl group with up to 4, and - if there are substituents on ring systems - still the alkyl and alkoxycarbonylalkyl group with up to 4 carbon atoms.
  • the dialkylamino group with a total of up to 6, preferably up to 2, carbon atoms may also be mentioned as further second substituents.
  • the glyoxylic acid derivatives of the formula 111 are also required as starting compounds.
  • Z stands for mono- or divalent cations of alkali and alkaline earth metals, as well as for the ammonium cation and the mono-, di- and trialkylammonium cations.
  • the alkyl radicals contain up to 2 carbon atoms.
  • Secondary amines are preferred as such, in particular cyclic amines such as pyrrolidine, piperidine, N-methylpiperazine and morpholine, but also open-chain amines such as dimethylamine and diethylamine.
  • Secondary amines are preferred as such, in particular cyclic amines such as pyrrolidine, piperidine, N-methylpiperazine and morpholine, but also open-chain amines such as dimethylamine and diethylamine.
  • the compounds mentioned are generally known.
  • the process according to the invention can be carried out with or without a solvent.
  • solvents which may be mentioned are: aliphatic or aromatic hydrocarbons, such as petroleum ether, benzene, toluene or xylene, aliphatic or aromatic halogenated hydrocarbons, such as carbon tetrachloride, chlorobenzene or dichlorobenzene, ethers, such as diethyl ether, tetrahydrofuran, dioxane or glycol dimethyl amide, dimethyethyl formamide, dimethylacetyl dimethyl amide, dimethylacetyl dimethyl amide, dimethylacetyl dimethyl amide, dimethylacetyl dimethyl amide, dimethylacetyl dimethyl amide, dimethylacetyl dimethyl amide, dimethylacetyl dimethyl amide, dimethylacetyl dimethyl amide, dimethylacetyl dimethyl amide, dimethylacetyl dimethyl amide, di
  • the process according to the invention is carried out at a temperature of from -30 to + 150 ° C., preferably from 20 to 80 ° C.
  • the o-hydroxyacetophenones (11) and the salt of glyoxylic acid (111) are generally used in stoichiometric amounts, ie in a ratio of 1: 2.
  • a small excess of a component, in particular the glyoxylic acid salt is used (e.g. 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 caused by acidic groups such as e.g. Carboxy groups, are substituted, it may be expedient to neutralize the acid groups by an excess of the amine.
  • the esterification of the dicarboxylic acids thus obtained can be carried out, for example, in a customary manner by stirring the dicarboxylic acid in a 4 to 100, preferably 10 to 50, 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 in crop protection are used to control 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 ingredients 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 known in the. Prepared in this way, for example 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. If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents.
  • 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, for example, also be used as auxiliary solvents.
  • liquid solvents aromatics, such as xylene, toluene, benzene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylene or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, alcohols, such as butanol or Glycol and their ethers and esters, ketones such as acetone, methyl ethylene ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water; liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as dichlorodifluoromethane or trichlorofluoromethane; as solid carriers: natural rock flour, such as
  • the formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
  • the active compounds 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 can be applied. 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 in the case of dressing, amounts of active compound of 10 mg to 10 g, preferably 100 mg to 3 g, are generally used per kilogram of seed.
  • active substance concentrations in the case of soil treatment, which can be carried out over the entire surface, in strips or in a punctiform manner, active substance concentrations of 1 to 1000 g of active substance per m 3 of soil, preferably 10 to 200 g per m3 , are required at the location of the expected action .
  • the compounds according to the invention inhibit the development of arthropods (arthrophodes).
  • the tests given below show the arthropod metamorphosis-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.
  • the morphological changes such as half pupated animals, incompletely hatched larvae or caterpillars, defective wings, puppal cuticles in adults and the death rate are assessed.
  • the sum of the morphological malformations and the mortality during development are rated.
  • 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 fed leaves of the forage plants, which are provided with a uniform spray coating of the active compound mixture of the selected concentration, so that an amount of active compound in ppm ("parts per million") is obtained on the leaves until 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 (alkylaryl polyglycol ether), and 975 parts by weight of water are added.
  • emulsifier alkylaryl polyglycol ether
  • the concentrate is diluted with water to the desired final concentration of the spray mixture.
  • 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. 096 means no infection and 100% the same degree of infection as for 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)

Description

Die Erfindung betrifft ein chemisch eigenantiges Verfahren zur Herstellung von Chromon-Derivaten, sowie Chromon-Derivate und deren Verwendung als Pflanzenschutzmittel.The invention relates to a chemically unique process for the production of chromone derivatives, as well as 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 (vgl. Elderfield, "Heterocyclic Compounds", Vol. 2, Seite 347), ferner ist noch bekannt, daß man auch aliphatische Aldehyde mit o-Hydroxyacetophenonen zu den entsprechenden 2-Alkylchromanonen umsetzen kann (vgl. DE-OS. 2535338). In beiden Fallen reagieren o-Hydroxyacetophenon und Aldehyd im Molverhältnis 1:1. Weiterhin ist noch bekannt, daß man aus o-Acylphenolen und Carbonsäure-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 in the presence of sodium hydroxide solution with o-hydroxyacetophenones to give 2-phenylchromanones (cf. Elderfield, "Heterocyclic Compounds", Vol. 2, page 347), and it is also known that aliphatic ones are also used Can react aldehydes with o-hydroxyacetophenones to the corresponding 2-alkylchromanones (cf. DE-OS. 2535338). 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 [vgl. 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 which is used worldwide [cf. R. Wegler, "Chemistry of crop protection and pesticides", 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-methoxybenzopyran [vgl. 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. the 2,2-dimethyl-6-methoxybenzopyran [cf. Chem. Eng. News 54, 19-20 (1976)].

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

Figure imgb0001
in welcher

  • R, R1 und R2 gleich oder verschieden sein können und für Wasserstoff, für Alkyl, Cycloalkyl, Alkenyl und Cycloalkenyl mit jeweils bis zu 8 Kohlenstoffatomen stehen, wobei die Alkyl- oder Cycloalkylreste gegebenenfalls durch Halogen, Cyan, Alkoxy- und Alkoxycarbonyl-Gruppen mit bis zu 4 Kohlenstoffatomen substituiert sein können; ferner für Phenyl, Naphthyl, Phenylalkyl und Naphthylalkyl mit 1 bis 4 Kohlenstoffatomen im Alkylteil stehen, wobei die genannten aromatischen Reste durch Halogen, Cyano, Alkyl-, Alkoxy-, Alkoxycarbonyl- und Alkoxycarbonylalkyl- mit bis zu 4 Kohlenstoffatomen und Di-alkyl-amino-Gruppen mit insgesamt bis zu 6 Kohlenstoffatomen substituiert sein können, ferner für gegebenenfalls durch Halogen oder Cyano substituiertes Alkoxy mit bis zu 4-Kohlenstoffatomen stehen; sodann für Phenoxy, Naphthoxy und Phenylalkoxy mit bis zu 4 Kohlenstoffatomen in Alkylteil stehen; weiterhin noch für Halogen, Cyano- und Hydroxy-Gruppen stehen, und schließlich für Alkoxycarbonyl- mit bis zu 4_und für Diälkylamino-Gruppen mit bis zu 3 Kohlenstoffatomen im Alkylteil stehen, wobei die beiden Alkylreste auch mit dem Aminostickstoffatom zu einem heterocyclischen Ring geschlossen sein können, und weiterhin zwei Reste
  • R und R1 zusammen mit 2 Kohlenstoffatomen des Benzolringsystems einen carbocyclischen oder heterocyclischen 5- oder 6-Ring bilden können, und
  • R3 für Wasserstoff und für Alkyl mit bis zu 4 Kohlenstoffen steht, wobei letzteres durch Halogen und Methoxy-Gruppen substituiert sein kann, ferner für Allyl, Cyclopentyl und Cyclohexyl, für Benzyl, Chlorbenzyl und für Phenyläthyl steht,

in einfacher Weise erhält, wenn man o-Hydroxyacetophenone der allgemeinen Formel II
Figure imgb0002
in welcher
  • R, R' und R2 die oben angegebene Bedeutung haben, mit Glyoxylsäure-Derivaten der allgemeinen Formel III
    Figure imgb0003
    in welcher
  • Z für ein- oder zweiwertige Kationen von Alkali- und Erdalkalimetallen, sowie für das Ammonium-, Mono-, Di- und Trialkylammonium-Kation stehen, wobei die Alkylreste jeweils bis zu 2 Kohlenstoff-. atome enthalten,

in Gegenwart von basischen Verbindungen im Temperaturbereich zwischen -30 und +150°C umsetzt und noch gegebenenfalls die dabei nach dem Ansäuern erhaltenen Carbonsäuren in an sich bekannter Weise in die entsprechenden Ester überführt.It has been found that the chromone derivatives of the general formula I
Figure imgb0001
 in which
  • R, R 1 and R 2 may be the same or different and represent hydrogen, alkyl, cycloalkyl, alkenyl and cycloalkenyl each having up to 8 carbon atoms, the alkyl or cycloalkyl radicals optionally being halogen, cyano, alkoxy and alkoxycarbonyl groups can be substituted with up to 4 carbon atoms; furthermore represent phenyl, naphthyl, phenylalkyl and naphthylalkyl with 1 to 4 carbon atoms in the alkyl part, the aromatic radicals mentioned being halogen, cyano, alkyl, alkoxy, alkoxycarbonyl and alkoxycarbonylalkyl having up to 4 carbon atoms and di-alkylamino Groups can be substituted with a total of up to 6 carbon atoms, furthermore represent alkoxy with up to 4 carbon atoms optionally substituted by halogen or cyano; then represent phenoxy, naphthoxy and phenylalkoxy with up to 4 carbon atoms in the alkyl part; furthermore stand for halogen, cyano and hydroxy groups, and finally for alkoxycarbonyl with up to 4_ and for dialkylamino groups with up to 3 carbon atoms in the alkyl part, where the two alkyl radicals can also be closed with the amino nitrogen atom to form a heterocyclic ring , and two remains
  • R and R 1 together with 2 carbon atoms of the benzene ring system can form a carbocyclic or heterocyclic 5- or 6-ring, and
  • R 3 stands for hydrogen and for alkyl with up to 4 carbons, the latter being able to be substituted by halogen and methoxy groups, also for allyl, cyclopentyl and cyclohexyl, for benzyl, chlorobenzyl and for phenylethyl,

obtained in a simple manner if o-hydroxyacetophenones of the general formula II
Figure imgb0002
 in which
  • R, R 'and R 2 have the meaning given above, with glyoxylic acid derivatives of the general formula III
    Figure imgb0003
     in which
  • Z stands for mono- or divalent cations of alkali and alkaline earth metals, as well as for the ammonium, mono-, di- and trialkylammonium cation, the alkyl radicals each having up to 2 carbon. contain atoms,

in the presence of basic compounds in the temperature range between -30 and + 150 ° C. and optionally converting the carboxylic acids obtained after acidification in a manner known per se into the corresponding esters.

Weiterhin wurden als neue Verbindungen die Chromon-Derivate der allgemeinen Formel la

Figure imgb0004
in welcher

  • R' für Wasserstoff, Chlor oder Methoxy steht, und
  • R" für Wasserstoff oder Methyl steht, gefunden.
Furthermore, the chromone derivatives of the general formula Ia were used as new compounds
Figure imgb0004
 in which
  • R 'represents hydrogen, chlorine or methoxy, and
  • R "represents hydrogen or methyl, found.

Die neuen Verbindungen der Formel la besitzen fungizide Eigenschaften; ferner hemmen sie die Entwicklung von Arthropoden. Sie sind daher als Pflanzenschutzmittel von Interesse.The new compounds of formula la 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 mit den Glyoxylsäure-Derivaten der Formel 111 in einer einfachen und überschaubaren Reaktion die Chromon-Derivate der Formel I ergeben und keine Chromanon-Verbindungen entstehen. 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 with the glyoxylic acid derivatives of the formula 111 give the chromone derivatives of the formula I in a simple and manageable reaction and that 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 Gegenwert von Pyrrolidin um und verestert die dabei erhaltene Dicarbonsäure anschließend mit Methanol, so kann der Reaktionsablauf durch das folgende Reaktionsschema wiedergegeben werden:

Figure imgb0005
If o-hydroxyacetophenone is reacted with the sodium salt of glyoxylic acid equivalent to 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 imgb0005

In der Formel II stehen R, R' 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 formula II, R, R '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 with one or more double bonds and up 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, R1 und 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 1 and R 2 furthermore 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.

R, R1 und R2 stehen weiterhin für Phenyl und Naphthyl, bevorzugt Phenyl.R, R 1 and R 2 furthermore represent phenyl and naphthyl, preferably phenyl.

Als gegebenenfalls substituierte Phenylalkyl- und Naphthylalkyl-Reste seien beispielhaft genannt: Benzyl, Phenyläthyl, Phenylpropyl, Phenylbutyl, Naphthylmethyl und Naphthyläthyl, bevorzugt Benzyl..Examples of optionally substituted phenylalkyl and naphthylalkyl radicals are: benzyl, phenylethyl, phenylpropyl, phenylbutyl, naphthylmethyl and naphthylethyl, preferably benzyl.

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

Als bevorzugte Phenylalkoxygruppen seien Benzyloxy, Phenyläthoxy, Phenylpropoxy, Phenylisopropoxy, Phenylbutoxy, Phenylisobutoxy und Phenyl-tert.-butoxy, genannt.Preferred phenylalkoxy groups include benzyloxy, phenylethoxy, phenylpropoxy, phenylisopropoxy, phenylbutoxy, phenylisobutoxy and phenyl tert-butoxy.

Als bevorzugte Alkoxycarbonylgruppen seien Methoxycarbonyl, Äthoxycarbonyl, Propoxycarbonyl, Isopropoxycarbonyl, genannt.Preferred alkoxycarbonyl groups are methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl.

Als bevorzugte Dialkylaminogruppen seien Dimethylamino, Diäthylamino, und Diisopropylamino, genannt. Es ist auch möglich, daß die beiden Alkylreste der Dialkylaminogruppe zu einem Ring geschlossen sind, wie beispielsweise Pyrrolidinyl, Piperidinyl.Dimethylamino, diethylamino and diisopropylamino may be mentioned as preferred dialkylamino groups. 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 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 form a carbocyclic or heterocyclic five- or six-membered ring with the two carbon atoms of the benzene ring on which they are located, such as, for example, a cyclopentene, cyclohexene, benzene, furan, dihydrofuran, thiophene , 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.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 . For example, the halogens such as fluorine, chlorine, bromine and Called iodine and the cyano group, also the alkoxy and alkoxycarbonyl group with up to 4, and - if there are substituents on ring systems - still the alkyl and alkoxycarbonylalkyl group with up to 4 carbon atoms. The dialkylamino group with a total of up to 6, preferably up to 2, carbon atoms may also be mentioned as further second substituents.

Die o-Hydroxyacetophenone der Formel II, die für das erfindungsgemäße Verfahren Verwendung finden können, sind bekannt (vgl. Beilstein, Handbuch der Organischen Chemie, H8, Seite 85 ff.). Beispielsweise seien 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-ß-Phenyläthyl-2-hydroxyacetophenon
  • 5-8-Phenylbutyl-2-hydroxyacetophenon
  • 3,5-Dibrom-2-hydroxyacetophenon
  • 4-Äthoxy-2-hydroxyacetophenon
  • 5-Äthoxycarbonyl-äthoxy-2-hydroxyacetophenon
  • 4-Methoxycarbony!-methoxy-2-hydroxyacetophenon
  • 4-Carboxymethyl-2-hydroxyacetophenon
  • 5-Nitro-2-hydroxyacetophenon
  • 3-Cyan-2-hydroxyacetophenon
  • 4-Trifiuormethyi-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-Phenoxy-2-hydroxyacetophenon
  • 4-p-Chlorphenoxy-2-hydroxyacetophenon
  • 5-p-Tolyl-2-hydroxyacetophenon
  • 1-Hydroxy-2-acetylnaphthalin
  • 2-Hydroxy-1-acetylnaphthalin
The o-hydroxyacetophenones of the formula II which can be used for the process according to the invention are known (cf. Beilstein, Handbuch der Organischen Chemie, H8, page 85 ff.). Examples include:
  • 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-ß-phenylethyl-2-hydroxyacetophenone
  • 5-8-phenylbutyl-2-hydroxyacetophenone
  • 3,5-dibromo-2-hydroxyacetophenone
  • 4-ethoxy-2-hydroxyacetophenone
  • 5-ethoxycarbonyl-ethoxy-2-hydroxyacetophenone
  • 4-methoxycarbony! Methoxy-2-hydroxyacetophenone
  • 4-carboxymethyl-2-hydroxyacetophenone
  • 5-nitro-2-hydroxyacetophenone
  • 3-cyan-2-hydroxyacetophenone
  • 4-trifluoromethyi-2-hydroxyacetophenone
  • 5-trifluoromethyl-2-hydroxyacetophenone
  • 3-trifluoromethyl-2-hydroxyacetophenone
  • 3-methoxycarbonyl-2-hydroxyacetophenone
  • 5-carboxy-2-hydroxyacetophenone
  • 5-dimethylamino-2-hydroxyacetophenone
  • 4-N-piperidinyl-2-hydroxyacetophenone
  • 3-phenoxy-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 111 benötigt. In der Formel III steht Z für ein- oder zweiwertige Kationen von Alkali- und Erdalkali-Metallen, sowie für das Ammonium-Kation und die Mono-, Di, und Trialkylammonium-Kationen. In den drei letztgenannten Fällen enthalten die Alkylreste bis zu 2 Kohlenstoffatome.The glyoxylic acid derivatives of the formula 111 are also required as starting compounds. In formula III, Z stands for mono- or divalent cations of alkali and alkaline earth metals, as well as for the ammonium cation and the mono-, di- and trialkylammonium cations. In the last three cases, the alkyl radicals 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, Piperidin, N-Methylpiperazin und, 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, piperidine, N-methylpiperazine and 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 gennant: 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. To carry out the process, all solvents are considered which are compared to the starting components and the end product are inert. Examples of solvents which may be mentioned are: aliphatic or aromatic hydrocarbons, such as petroleum ether, benzene, toluene or xylene, aliphatic or aromatic halogenated hydrocarbons, such as carbon tetrachloride, chlorobenzene or dichlorobenzene, ethers, such as diethyl ether, tetrahydrofuran, dioxane or glycol dimethyl amide, dimethyethyl formamide, dimethylacetyl dimethyl amide, dimethylacetyl dimethyl amide, dimethylacetyl dimethyl amide, dimethylacetyl dimethyl amide, dimethylacetyl dimethyl amide, dimethylacetyl dimethyl amide, dimethylacetyl dimethyl amide, dimethylacetyl dimethyl amide, dimethylacetyl dimethyl amide, dimethylacetyl dimethyl amide, dimethylacetyl dimethyl amide, dimethylacetyl dimethyl amide, dimethylacetyl dimethyl amide, such as dimethylacetyl dimethyl amide, dimethylacetyl dimethyl amide, dimethylacetyl dimethyl amide, such as dimethyl ether, dimethylacetyl dimethyl amide, such as dimethyl acetate, and N-methylpyrrolidone, further esters such as ethyl acetate, nitriles such as acetonitrile, propiononitrile, and alcohols such as methanol, ethanol and glycol monomethyl ether, and finally water.

Das erfindungsgemäße Verfahren wird bei einer Temperatur von -30 bis +150°C, bevorzugt von 20 bis 80°C, durchgeführt.The process according to the invention is carried out at a temperature of from -30 to + 150 ° C., preferably from 20 to 80 ° C.

Zur Durchführung des erfindungsgemäßen Verfahrens werden im allgemeinen die o-Hydroxyacetophenone (11) und das Salz der Glyoxylsäure (111) 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 Überschuß des Amins die sauren Gruppen zu neutralisieren.To carry out the process according to the invention, the o-hydroxyacetophenones (11) and the salt of glyoxylic acid (111) are generally used in stoichiometric amounts, ie in a ratio of 1: 2. For the implementation of the method 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 (e.g. 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 caused by acidic groups such as e.g. Carboxy groups, are substituted, it may be expedient to neutralize the acid groups by 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 erhalt dann die Dicarbonsäure-Verbindungen der Formel 1, 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 1 are then obtained, where R 3 is hydrogen.

Die Veresterung der so 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 thus obtained can be carried out, for example, in a customary manner by stirring the dicarboxylic acid in a 4 to 100, preferably 10 to 50, 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 beispielweise 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-Carbomethoxy-3-carbomethoxymethyl-7-phenyl-chromon
  • 2-Carbomethoxy-3-carbomethoxymethyl-5-methoxy-chromon
  • 2-Carbomethoxy-3-carbomethoxymethyl-6-methoxy-chromon
  • 2-Carbomethoxy-3-carbomethoxymethyl-7-methoxy-chromon
  • 2-Carbomethoxy-3-carbomethoxymethyl-8-methoxy-chromon
  • 2-Carbomethoxy-3-carbomethoxymethyl-6-chlor-8-methyl-chromon
  • 2-Carbomethoxy-3-carbomethoxymethyl-7,8-dimethoxy-chromon
  • 2-Carbomethoxy-3-carbomethoxymethy)-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-propoxy-3-carbo-propoxymethylchromon
  • 2-Carbo-isopropoxy-3-carbo-isopropoxymethylchromon
  • 2-Carbo-butoxy-3-carbo-butoxymethylchromon
  • 2-Carbo-sek.-butoxy-3-carbo-sek. butoxymethylchromon
  • 2-Carbo-iso-butoxy-3-carbo-iso=butoxymethylchromon
  • 2-Carbo-tert.-butoxy-3-carbo-tert.-butoxymethy)chromon
  • 2-Carbo-benzyloxy-3-carbo-benzyloxymethylchromon
  • 2-Carbo-phenäthoxy-3-carbo-phenäthoxymethylchromon
  • 2-Carbo-cyclopentyloxy-3-carbo-cyclopentyloxymethylchromon
  • 2-Carbo-cyclohexyloxy-3-carbo-cyclohexyloxymethylchromon
  • 2-Carbo-allyloxy-3-carbo-allyloxymethylchromon
  • 2-Carbo-p-chlorbenzyloxy-3-carbo-p-chlorbenzyloxymethylchromon
  • 2-Carbo-2'-methoxyäthoxy-3-carbo-2'-methoxyäthoxymethylchromon
  • 2-Carbo-2'-bromäthoxy-3-carbo-2'-bromäthoxymethylchromon
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 chromone
  • 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-methyl-chromon
  • 2-carbomethoxy-3-carbomethoxymethyl-7-methyl-chromon
  • 2-carbomethoxy-3-carbomethoxymethyl-6-isobutyl chromon
  • 2-carbomethoxy-3-carbomethoxymethyl-6-cyclopentyl chromon
  • 2-carbomethoxy-3-carbomethoxymethyl-7-phenyl-chromon
  • 2-carbomethoxy-3-carbomethoxymethyl-5-methoxy-chromon
  • 2-carbomethoxy-3-carbomethoxymethyl-6-methoxy-chromon
  • 2-carbomethoxy-3-carbomethoxymethyl-7-methoxy-chromon
  • 2-carbomethoxy-3-carbomethoxymethyl-8-methoxy-chromon
  • 2-carbomethoxy-3-carbomethoxymethyl-6-chloro-8-methyl-chromon
  • 2-carbomethoxy-3-carbomethoxymethyl-7,8-dimethoxy-chromon
  • 2-carbomethoxy-3-carbomethoxymethy) -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-propoxy-3-carbo-propoxymethylchromone
  • 2-carbo-isopropoxy-3-carbo-isopropoxymethylchromone
  • 2-carbo-butoxy-3-carbo-butoxymethylchromone
  • 2-carbo-sec-butoxy-3-carbo-sec. butoxymethylchromone
  • 2-carbo-iso-butoxy-3-carbo-iso = butoxymethylchromone
  • 2-carbo-tert-butoxy-3-carbo-tert-butoxymethy) chromon
  • 2-carbo-benzyloxy-3-carbo-benzyloxymethylchromone
  • 2-carbo-phenethoxy-3-carbo-phenethoxymethylchromone
  • 2-carbo-cyclopentyloxy-3-carbo-cyclopentyloxymethylchromon
  • 2-carbo-cyclohexyloxy-3-carbo-cyclohexyloxymethylchromon
  • 2-carbo-allyloxy-3-carbo-allyloxymethylchromon
  • 2-carbo-p-chlorobenzyloxy-3-carbo-p-chlorobenzyloxymethylchromon
  • 2-carbo-2'-methoxyethoxy-3-carbo-2'-methoxyethoxymethylchromone
  • 2-carbo-2'-bromoethoxy-3-carbo-2'-bromoethoxymethylchromone

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 in crop protection are used to control 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 Wirkstoffe 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 ingredients 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 Strecktmittel können z.B. auch organische Lösungsmittel als Hilfslösungsmittel verwendet werden. Als flüssige Lösungsmittel kommen im wesentlichen in Frage: Aromaten, wie Xylol, Toluol, Benzol oder Alkylnaphthaline, chlorierte Aromaten 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, Methyläthylenketon, 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: natürliche Gesteinsmehle, wie Kaoline, Tonerden, Talkum, Kreide, Quartz, Attapulgit, Montmorillonit oder Diatomeenerde und synthetische Gesteinsmehle, wie hochdisperse Kieselsäure, Aluminiumoxid und Silikate; als Emulgiermittel; nichtionogene und anionische Emulgatoren, wie Polyoxyäthylen-Fettsäure-Ester, Polyoxyäthylen-Fettalkohol-Ather, z.B. Alkylarylpolyglykoläther, 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 known in the. Prepared in this way, for example 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. If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, benzene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylene or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, alcohols, such as butanol or Glycol and their ethers and esters, ketones such as acetone, methyl ethylene ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water; liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as dichlorodifluoromethane or trichlorofluoromethane; as solid carriers: natural rock flour, such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powder, such as highly disperse silica, aluminum oxide and silicates; as an emulsifier; nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; as dispersing agents: eg lignin sulfite liquor and methyl cellulose.

Die Formulierungen enthalten im allgemeinen zwischen 0,1 und 95 Gewichtsprozent Wirkstoff, vorzugsweise zwischen 0,5 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 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 can be applied. 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 un 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 10g, vorzugsweise 100 mg bis 3 g zur Anwendung. Bei der Boden behandlung, 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 g, are generally used per kilogram of seed. In the case of soil treatment, which can be carried out over the entire surface, in strips or in a punctiform manner, active substance concentrations of 1 to 1000 g of active substance per m 3 of soil, preferably 10 to 200 g per m3 , are required at the location of the expected action .

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

Durch den im folgenden angegebenen Versuche wird die arthropodenmetamorphosehemmende 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 metamorphosis-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 and the death rate are assessed. The sum of the morphological malformations and the mortality during development are rated.

Beispiel AExample A

Entwicklungshemmende Wirkung/Fraßtest

Figure imgb0006
Developmental inhibitory effect / feeding test
Figure imgb0006

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 fed leaves of the forage plants, which are provided with a uniform spray coating of the active compound mixture of the selected concentration, so that an amount of active compound in ppm ("parts per million") is obtained on the leaves until 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 Sproßbehandlungs-Test/Getreidemehltau/protektivShoot treatment test / powdery mildew / protective (blattzerstörende Mykose)(leaf-destroying mycosis)

Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung nimmt man 0,25 Gewichsteile Wirkstoff in 25 Gewichtsteilen Dimethylformamid und 0,06 Gewichtsteilen Emulgator (Alkylarylpolyglykoläther) auf und gibt 975 Gewichtsteile Wasser hinzu. Das Konzentrat verdünnt man mit Wasser 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 (alkylaryl 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, spray the single-leafed barley seedlings of the blackbird variety with the preparation of the active ingredient as dewy. After drying, the barley is dusted plants with spores of Erysiphe graminis var. hordei.

Nach 6 Tagen Verweilzeit der Pflanzen bei einer Temperaturen 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 096 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 an air 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. 096 means no infection and 100% the same degree of infection as for 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 imgb0007
Active substances, active substance concentrations in the spray mixture and degrees of infestation are shown in the table below:
Figure imgb0007

Beispiel 1example 1

Figure imgb0008
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 imgb0008
 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 is 92% of theory.

Beispiel 1 aExample 1 a

Man arbeitet wie in Beispiel 1 angegeben, erwärmt aber nach dem Zusammengeben der Ausgangstoffe währen 30 Minuten auf 95°C. Die Aufarbeitung ergibt 112 g 2-Carboxy-3-carboxymethyl- chromon, das sind 82% der Theorie.The procedure is as given in Example 1, but after the starting materials have been combined, the mixture is heated to 95 ° C. for 30 minutes. The workup gives 112 g of 2-carboxy-3-carboxymethylchromon, which is 82% of theory.

Beispiel 2Example 2

Figure imgb0009
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 imgb0009
 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)(Esterification reaction)

Figure imgb0010
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.
Figure imgb0010
 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 suction filtered. 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 of thionyl chloride are added in about 10 minutes, the temperature being kept 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 imgb0011
Figure imgb0011

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. 82-84°C.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, mp. 82-84 ° C.

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

Figure imgb0012
herstellen.
Figure imgb0013
 In a manner similar to that described in Examples 1 to 4, the following compounds of the general formula I can be
Figure imgb0012
 produce.
Figure imgb0013

Claims (6)

1. Process for the preparation of chromone derivatives of the general formula I
Figure imgb0018
in which
R, R' and R1 can be identical or different and represent hydrogen, and alkyl, cycloalkyl, alkenyl and cycloalkenyl with in each case up to 8 carbon atoms, the alkyl or cycloalkyl radicals optionally being able to be substituted by halogen, cyano, alkoxy, and alkoxycarbonyl groups with up to 4 carbon atoms; and also phenyl, naphthyl, phenylalkyl and naphthylalkyl with 1 to 4 carbon atoms in the alkyl part, the named aromatic radicals being able to be substituted by halogen, cyano, and alkyl, alkoxy, alkoxycarbonyl and alkoxycarbonylalkyl groups with up to 4 carbon atoms and dialkylamino groups with a total of up to 6 carbon atoms; and also alkoxy, optionally substituted by halogen or cyano, with up to 4 carbon atoms; also phenoxy, naphthoxy and phenylalkoxy with up to 4 carbon atoms in the alkyl part, furthermore also halogen, cyano and hydroxy groups and finally alkoxycar-' bonyl groups with up to 4 carbon atoms in the alkyl part and dialkylamino groups with up to 3 carbon atoms in the alkyl part, the two alkyl radicals also being able to be cyclised, with the amino- nitrogen atom, to form a heterocyclic ring, and furthermore two radicals
R and R1 together with 2 carbon atoms of the benzene ring system can form a carbocyclic or heterocyclic 5-membered or 6-membered ring and
R3 represents hydrogen and alkyl with up to 4 carbon atoms, alkyl being able to be substituted by halogen and methoxy groups, also allyl, cyclopentyl and cyclohexyl, and benzyl, chlorobenzyl, and phenylethyl, characterised in that o-hydroxyacetophenones of the general formula II
Figure imgb0019
in which
R, R1 and R2 have the abovementioned meaning, are reacted with glyoxylic acid derivatives of the general formula III
Figure imgb0020
in which
Z represents monovalent or divalent cations of alkali metals and alkaline earth metals, as well as the ammonium cation and the monoalkylammonium, dialkylammonium and trialkylammonium cation, the alkyl radicals in each case containing up to 2 carbon atoms,

in the presence of basic compounds in the temperature range of between -30 and +150°C and in addition, if desired, the carboxylic acids obtained after acidification are converted in a manner which is in itself known into the corresponding esters.
2. Process according to claim 1, characterised in that secondary amines are used as basic compounds.
3. Process according to claim 1, characterised in that the reaction is carred out in the temperature range of between +20 and +80°C.
4. Chromone derivatives of the general formula la
Figure imgb0021
in which
R' represents hydrogen, chlorine or methoxy, and
R" represents hydrogen or methyl.
5. Fungicidal agents and agents which inhibit the development of arthropods, characterised in that they contain at least one chromone derivative according to claim 4.
6. Use of chromone derivatives according to claim 4 for combating fungi and for inhibiting the development of arthropods.
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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