EP0000934B1 - 5-indanyl esters of n-alkyl carbamic acid, processes for their preparation and their use as pesticides - Google Patents

5-indanyl esters of n-alkyl carbamic acid, processes for their preparation and their use as pesticides Download PDF

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Publication number
EP0000934B1
EP0000934B1 EP78100703A EP78100703A EP0000934B1 EP 0000934 B1 EP0000934 B1 EP 0000934B1 EP 78100703 A EP78100703 A EP 78100703A EP 78100703 A EP78100703 A EP 78100703A EP 0000934 B1 EP0000934 B1 EP 0000934B1
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Prior art keywords
alkyl
spp
carbamic acid
hydroxy
formula
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German (de)
French (fr)
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EP0000934A1 (en
Inventor
Detlef Dr. Grotkopp
Karlfried Dr. Wedemeyer
Wilhelm Dr. Brandes
Hans Dr. Scheinpflug
Peter Dr. Roessler
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Bayer AG
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Bayer AG
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/22—O-Aryl or S-Aryl esters thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/40—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings
    • C07C271/42—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C271/44—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
    • C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
    • C07C37/0555—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group being esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • C07C37/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon unsaturated bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane

Definitions

  • the present invention relates to new indan-5-yl-N-alkyl-carbamic acid esters, several processes for their preparation and their use as crop protection agents.
  • N-methyl-carbamic acid ester of 5-hydroxyindane is insecticidal (cf. US Pat. Nos. 2,870,057 and 3,084,096). Furthermore, it has already become known that the N-trichloromethylthiotetrahydrophthalimide has strong fungicidal properties (cf. Science, Vol. 115, p. 84 (1952)). However, this active ingredient, which is important in practice, has only a protective effect.
  • the compounds have strong fungicidal and arthropod-inhibiting properties and can therefore be used as crop protection agents.
  • the indan-5-yl-N-alkyl-carbamates according to the invention have a surprisingly high fungicidal activity and are superior to the previously known N-trichloromethylthio-tetrahydropthalimide even at low application rates. Furthermore, they can be used not only as protective, but also as curative agents.
  • the substances according to the invention thus represent an enrichment of the technology. For use as crop protection agents it is of interest that the active substances are able to inhibit the development of arthropods.
  • reaction sequence according to process a) can be represented by the following formula:
  • R2 preferably represents hydrogen and lower alkyl having 1 to 4 carbon atoms and R 3 and R 4 chlorine and lower alkyl having 1 to 4 carbon atoms.
  • the compounds can be analogous to previously known processes (cf.
  • the starting materials, phosgene and alkyl isocyanate required for process a), or phosgene and alkylamine for process variants b) and c), which are also required for the preparation of the compounds of formula (I) according to the invention, are generally known.
  • Those alkyl isocyanates or alkyl amines which contain an alkyl radical having 1 to 4 carbon atoms are preferably used. These include: methyl isocyanate, ethyl isocyanate, butyl isocyanate, and the following amines: methylamine, ethylamine, isopropylamine, butylamine, isobutylamine.
  • the radical R ' preferably denotes alkyl having 1 to 4 carbon atoms.
  • the reaction according to process a) can be carried out in inert solvents.
  • inert solvents e.g. Hydrocarbons, such as gasoline and benzene, chlorinated hydrocarbons, such as chlorobenzene, but also ethers, such as dioxane, or mixtures of these solvents.
  • the reaction is carried out by adding a tertiary amine, e.g. Triethylamine or diazabicyclooctane, catalyzed.
  • the reaction temperatures can be varied within a wide range. In general, however, you will work between 0 and 150 ° C, preferably between 20 and 110 ° C.
  • the 5-hydroxy-indane of the formula (II) is advantageously in the presence of inert solvents, such as aromatic, optionally chlorinated, hydrocarbons, e.g. Benzene, toluene, xylene or chlorobenzene, with an excess of phosgene in the chlorocarbonic acid ester.
  • inert solvents such as aromatic, optionally chlorinated, hydrocarbons, e.g. Benzene, toluene, xylene or chlorobenzene, with an excess of phosgene in the chlorocarbonic acid ester.
  • the hydrochloric acid formed is bound by dropwise addition of a base, advantageously sodium hydroxide, and the pH of the reaction solution is thus kept below 7.
  • a base advantageously sodium hydroxide
  • the chlorocarbonic acid ester is reacted with the equivalent amount of alkylamine either after isolation or directly in the reaction solution obtained. It is also convenient to work in the presence of inert solvents such as aromatic and aliphatic, optionally chlorinated hydrocarbons, such as benzene, toluene, chlorobenzene, gasoline, carbon tetrachloride, or ethers, such as dioxane.
  • inert solvents such as aromatic and aliphatic
  • optionally chlorinated hydrocarbons such as benzene, toluene, chlorobenzene, gasoline, carbon tetrachloride, or ethers, such as dioxane.
  • the reaction temperatures can in turn be varied within a certain range; one generally works between -20 and + 20 ° C, preferably between -10 and + 10 ° C.
  • the 5-hydroxy in the formula (11) with the equivalent amount of phosgene to the bis (indanyl) carbonic acid ester is expediently carried out in inert solvents, such as aromatic hydrocarbons, for example benzene and toluene, the hydrochloric acid formed being bound by adding a base, preferably alkali metal hydroxide.
  • the pH of the reaction solution should be around 8.
  • the reaction temperature can vary within a substantial range, it is generally between 0 and 100 ° C, preferably between +20 and 60 ° C.
  • the carbonate formed in the first stage is then broken down with alkylamine. It is convenient to work without solvents. However, the reaction can also be carried out in solvents.
  • the reaction temperatures are between -30 and + 40 ° C, preferably between -10 and + 20 ° C.
  • the active substances according to the invention have a strong 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, Basidiomycetes, Deuteromycetes.
  • the active compounds according to the invention have a broad spectrum of activity and can be used against parasitic fungi which attack above-ground parts of plants or attack the plants from the ground, and against seed-borne pathogens. They are particularly effective against parasitic fungi on above-ground parts of plants.
  • the active compounds according to the invention can be used with particularly good success as crop protection agents for controlling Venturia species, for example for controlling apple scab (Fusicladium dendriticum). It should be noted that the active ingredients are not only protective, but also curative.
  • Thysanoptera e.g. Hercinothrips femoralis, Thrips tabaci.
  • Homoptera e.g. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Rhoralosobusumumisis, pad.
  • Homoptera e.g. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Rhoralosobusumumisis,
  • Nephotettix cincticeps Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp.
  • Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
  • Acarina e.g. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp.,. Chori ., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.
  • Acarina e.g. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp.
  • 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 made in a known manner, e.g. 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, e.g. organic solvents can also be used as auxiliary 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, e.g.
  • Petroleum fractions oil fractions, alcohols, such as butanol or glycol, and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methytisobutyiketone 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 pressure, e.g.
  • 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, e.g.
  • the active compounds according to the invention can be present in the formulations in a mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, herbicides, bird repellants, growth agents, plant nutrients and agents which improve soil structure.
  • active compounds such as fungicides, insecticides, acaricides, nematicides, herbicides, bird repellants, growth agents, plant nutrients and agents which improve soil structure.
  • 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 in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. They are used in the usual way, e.g. by pouring, spraying, spraying, dusting, scattering, dry pickling, wet pickling, wet pickling, slurry pickling or incrusting.
  • the active compound concentrations in the use forms can be varied within a substantial range. They are generally between 0.1 and 0.00001 percent by weight, preferably between 0.05 and 0.0001%.
  • active ingredient 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required.
  • the compounds according to the invention inhibit the development of arthropods.
  • the experiments described below demonstrate the arthropod development-inhibiting activity of the compounds according to the invention.
  • the morphological changes such as half pupated animals, incompletely hatched larvae or caterpillars, defective wings, pupal cuticles in adults, etc., are assessed as malformations.
  • the compounds according to the invention also have an insecticidal activity.
  • Emulsifier 0.3 part by weight of alkyl aryl polyglycol ether
  • the amount of active ingredient required for the desired active ingredient concentration in the spray liquid is mixed with the stated amount of solvent and the concentrate is diluted with the stated amount of water which contains the additives mentioned.
  • the spray liquid is used to spray young apple seedlings, which are in the 4- to 6-leaf stage, until they drip wet.
  • the plants remain in the greenhouse for 24 hours at 20 ° C. and a relative humidity of 70%. They are then inoculated with an aqueous conidia suspension of the apple scab pathogen (Fusicladium dendriticum) and incubated for 18 hours in a humid chamber at 18 to 20 ° C. and 10096 relative atmospheric humidity.
  • the infestation of the seedlings is determined 15 days after the inoculation.
  • the rating values received are converted into percent infestation. 0% means no infection, 100% means that the plants are completely infected.
  • Emulsifier 0.3 part by weight of alkyl aryl polyglycol ether
  • the amount of active ingredient required for the desired active ingredient concentration in the spray liquid is mixed with the stated amount of solvent and the concentrate is diluted with the stated amount of water which contains the additives mentioned.
  • Young apple seedlings which are in the 4 to 6 leaf stage, are inoculated with an aqueous conidia suspension of the apple scab pathogen (Fusicladium dentriticum) and incubated for 18 hours in a humid chamber at 18 to 20 ° C. and 100% relative atmospheric humidity. The plants then come into the greenhouse. They dry up.
  • apple scab pathogen Feusicladium dentriticum
  • the plants are sprayed with the spray liquid, which is produced in the manner described above, to the point of dripping wet. Then the plants come back into the greenhouse.
  • the infestation of the apple seedlings is determined 15 days after the inoculation.
  • the rating values received are converted into percent infestation. 0% means no infection, 100% means that the plants are completely infected.
  • the compound according to the invention corresponding to preparation example 1 shows a good effect which is superior to the comparative preparation given in the prior art.
  • Test animals Plutella maculipennis (caterpillars in the 4th stage of development) 20 pieces
  • 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 fodder plants, which are provided with a uniform spray coating of the active compound mixture of the selected concentration, so that the stated amounts of active compound in ppm (parts per million) are obtained on the leaves until the development of the Imago.
  • the compound according to the invention according to Preparation Example 1 shows good effectiveness. It outperforms the known comparative 2,2-dimethyl-6-methoxy-benzopyran.
  • Lining synthetic lining (carrot powder with yeast powder)
  • Emulsifier 5 parts by weight of alkylaryl polyglycol ether
  • active compound 4 parts by weight of active compound are mixed with the stated amount of solvent, emulsifier and enough water to produce a 1% mixture which is diluted with water to the desired concentration.
  • the eggs of the test animals are placed on a bowl of artificial feed into which the selected concentration of the active ingredient mixture is incorporated, so that the specified amount of active ingredient in ppm (parts per million) is reached.
  • the development up to the hatching of the flies is observed.
  • the active compounds according to the preparation examples according to the invention show good activity.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
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Description

Die vorliegende Erfindung betrifft neue Indan-5-yl-N-alkyl-carbaminsäureester, mehrere Verfahren zu ihrer Herstellung sowie ihre Verwendung als Pflanzenschutzmittel.The present invention relates to new indan-5-yl-N-alkyl-carbamic acid esters, several processes for their preparation and their use as crop protection agents.

Es ist bereits bekannt geworden, daß der N-Methyl-carbaminsäureester des 5-Hydroxy-indans insektizid wirksam ist (vgl. die US-Patentschriften 2 870 057 und 3 084 096). Weiterhin ist bereits bekannt geworden, daß das N-Trichlormethylthiotetrahydrophthalimid starke fungizide Eigenschaften aufweist (vgl. Science, Bd. 115, S. 84 (1952)). Dieser in der Praxis wichtige Wirkstoff hat jedoch nur eine protektive Wirksamkeit.It has already been known that the N-methyl-carbamic acid ester of 5-hydroxyindane is insecticidal (cf. US Pat. Nos. 2,870,057 and 3,084,096). Furthermore, it has already become known that the N-trichloromethylthiotetrahydrophthalimide has strong fungicidal properties (cf. Science, Vol. 115, p. 84 (1952)). However, this active ingredient, which is important in practice, has only a protective effect.

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 (Chem. Eng. News 54, 19-20 (1976)).Active ingredients that inhibit the metamorphosis of arthropods have only recently been of interest in crop protection. 2,2-dimethyl-6-methoxybenzopyran (Chem. Eng. News 54, 19-20 (1976)).

Es wurden nun als neue Stoffe die Indan-5-yl-N-alkyl-carbaminsäureester der Formel

Figure imgb0001
in welcher

  • R' für Alkyl steht,
  • R2 für Wasserstoff oder Alkyl steht, und
  • R3 und R4 für Chlor oder Alkyl stehen,

gefunden.The indan-5-yl-N-alkyl-carbamic acid esters of the formula have now been added
Figure imgb0001
 in which
  • R 'represents alkyl,
  • R 2 represents hydrogen or alkyl, and
  • R 3 and R 4 represent chlorine or alkyl,

found.

Die Verbindungen weisen starke fungizide und die Entwicklung von Arthropoden hemmende Eigenschaften auf und sind daher als Pflanzenschutzmittel verwendbar.The compounds have strong fungicidal and arthropod-inhibiting properties and can therefore be used as crop protection agents.

Weiterhin wurde gefunden, daß man die Indan-5-yl-N-alkyl-carbaminsäureester der Formel (I)
erhält, wenn man

  • a) 5-Hydroxy-indane der Formel
    Figure imgb0002
    in welcher
    • R2, R3 und R4 die oben angegebene Bedeutung besitzen, mit einem Alkylisocyanat umsetzt,
      oder
  • b) 5-Hydroxy-indane der Formel (11) in einer ersten Stufe mit einem Überschuß an Phosgen in den entsprechenden Chlorkohlensäureester überführt und diesen mit Alkylamin umsetzt,
    oder
  • c) 5-Hydroxy-indane der Formel (11) in einer ersten Stufe mit der äquivalenten Menge Phosgen zu dem entsprechenden Bis-(indanyl)-carbonat umsetzt und dieses in einer zweiten Stufe mit Alkylamin aufspaltet.
It was also found that the indan-5-yl-N-alkyl-carbamic acid esters of the formula (I)
get when one
  • a) 5-hydroxy-indanes of the formula
    Figure imgb0002
     in which
    • R 2 , R 3 and R 4 have the meaning given above, reacted with an alkyl isocyanate,
      or
  • b) converting 5-hydroxy-indanes of the formula (11) in a first stage with an excess of phosgene into the corresponding chlorocarbonic acid ester and reacting this with alkylamine,
    or
  • c) 5-Hydroxy-indanes of the formula (11) are reacted in a first stage with the equivalent amount of phosgene to give the corresponding bis- (indanyl) carbonate and this is split in a second stage with alkylamine.

Die erfindungsgemäßen Indan-5-yl-N-alkyl-carbamate weisen eine überraschend hohe fungizide Wirkung auf und sind dem vorbekannten N-Trichlormethylthio-tetrahydropthalimid auch bei niedrigen Aufwandmengen überlegen. Weiterhin können sie nicht nur als protektive, sondern auch als kurative Mittel Verwendung finden. Die erfindungsgemäßen Stoffe stellen somit eine Bereicherung der Technik dar. Für die Verwendung als Pflanzenschutzmittel ist von Interesse, daß die Wirkstoffe die Entwicklung von Arthropoden zu hemmen vermögen.The indan-5-yl-N-alkyl-carbamates according to the invention have a surprisingly high fungicidal activity and are superior to the previously known N-trichloromethylthio-tetrahydropthalimide even at low application rates. Furthermore, they can be used not only as protective, but also as curative agents. The substances according to the invention thus represent an enrichment of the technology. For use as crop protection agents it is of interest that the active substances are able to inhibit the development of arthropods.

Verwendet man 5-Hydroxy-3,3,6,7-tetramethyl-indan und Methylisocyanat als Ausgangsstoffe, so läßt sich der Reaktionsablauf gemäß Verfahren a) durch folgendes Formelschema wiedergeben:

Figure imgb0003
If 5-hydroxy-3,3,6,7-tetramethyl-indane and methyl isocyanate are used as starting materials, the reaction sequence according to process a) can be represented by the following formula:
Figure imgb0003

Verwendet man 5-Hydroxy-3,3,6,7-tetramethyl-indan, Phosgen und Methylamin als Ausgangsstoffe, so läßt sich der Reaktionsablauf gemäß Verfahren b) durch das folgende Formelschema wiedergeben:

Figure imgb0004
Figure imgb0005
 If 5-hydroxy-3,3,6,7-tetramethyl-indane, phosgene and methylamine are used as starting materials, the course of the reaction according to process b) can be represented by the following formula:
Figure imgb0004
Figure imgb0005

Verwendet man 5-Hydroxy-3,3,6,7-tetramethyf-indan, Phosgen und Methylamin als Ausgangsstoffe, läßt sich der Reaktionsablauf gemäß Verfahren c) durch das folgende Formelschema wiedergeben:

Figure imgb0006
Figure imgb0007
 If 5-hydroxy-3,3,6,7-tetramethyf-indane, phosgene and methylamine are used as starting materials, the course of the reaction according to process c) can be represented by the following formula:
Figure imgb0006
Figure imgb0007

Die als Ausgangsstoffe verwendeten 5-Hydroxy-indane sind durch die oben angegebene Formel (11) eindeutig charakterisiert. In dieser Formel stehen R2 vorzugsweise für Wasserstoff und für niederes Alkyl mit 1 bis 4 C-Atomen und R3 und R4 für Chlor und für niederes Alkyl mit 1 bis 4 C-Atomen. Die Verbindungen lassen sich in Analogie zu bisher bekanntgewordenen Verfahren (vgl. Houben-Weyl, "Methoden der organischen Chemie", 4. Auf!., Band 6/1 c, Seite 987 (1976) und die DT―OS 2 603 835 [Le A 16 930]) durch Umsetzung entsprechender Phenole, wie z.B. 2,3-Dimethylphenol, mit Butadienen, wie z.B. Isopren oder 2,3-Dimethylbutadien-(1,3), in Gegenwart von Phosphorsäure bei Temperaturen von etwa 100 bis 150°C herstellen.The 5-hydroxy-indanes used as starting materials are clearly characterized by the formula (11) given above. In this formula, R2 preferably represents hydrogen and lower alkyl having 1 to 4 carbon atoms and R 3 and R 4 chlorine and lower alkyl having 1 to 4 carbon atoms. The compounds can be analogous to previously known processes (cf. Houben-Weyl, "Methods of Organic Chemistry", 4th edition!, Volume 6/1 c, page 987 (1976) and the DT ― OS 2 603 835 [ Le A 16 930]) by reacting appropriate phenols, such as 2,3-dimethylphenol, with butadienes, such as isoprene or 2,3-dimethylbutadiene- (1,3), in the presence of phosphoric acid at temperatures of about 100 to 150 ° Create C.

Die weiterhin für die Herstellung der erfindungsgemäßen Verbindungen der Formel (I) benötigten Ausgangsstoffe, Phosgen und Alkylisocyanat für Verfahren a), bzw. Phosgen und Alkylamin für die Verfahrensvarianten b) und c), sind allgemein bekannt. Bevorzugt werden solche Alkylisocyanate bzw. Alkylamine verwendet, die einen Alkylrest mit 1 bis 4 C-Atomen enthalten. Zu nennen sind hier: Methylisocyanat, Äthylisocyanat, Butylisocyanat, sowie die folgenden Amine: Methylamin, Äthylamin, Isopropylamin, Butylamin, Isobutylamin. Demgemäß bedeutet in Formel (I) der Rest R' vorzugsweise Alkyl mit 1 bis 4 C-Atomen.The starting materials, phosgene and alkyl isocyanate required for process a), or phosgene and alkylamine for process variants b) and c), which are also required for the preparation of the compounds of formula (I) according to the invention, are generally known. Those alkyl isocyanates or alkyl amines which contain an alkyl radical having 1 to 4 carbon atoms are preferably used. These include: methyl isocyanate, ethyl isocyanate, butyl isocyanate, and the following amines: methylamine, ethylamine, isopropylamine, butylamine, isobutylamine. Accordingly, in formula (I) the radical R 'preferably denotes alkyl having 1 to 4 carbon atoms.

Die Reaktion nach Verfahren a) kann in inerten Lösungsmitteln vorgenommen werden. Hierfür eignen sich z.B. Kohlenwasserstoffe, wie Benzin und Benzol, chlorierte Kohlenwasserstoffe, wie Chlorbenzol, aber auch Äther, wie Dioxan, oder Mischungen aus diesen Lösungsmitteln. Die Umsetzung wird durch Zugabe eines tertiären Amins, z.B. Triäthylamin oder Diazabicyclooctan, katalysiert. Die Reaktionstemperaturen können in einem größeren Bereich variiert werden. Im allgemeinen wird man jedoch zwischen 0 und 150°C arbeiten, vorzugsweise zwischen 20 und 110°C.The reaction according to process a) can be carried out in inert solvents. For this, e.g. Hydrocarbons, such as gasoline and benzene, chlorinated hydrocarbons, such as chlorobenzene, but also ethers, such as dioxane, or mixtures of these solvents. The reaction is carried out by adding a tertiary amine, e.g. Triethylamine or diazabicyclooctane, catalyzed. The reaction temperatures can be varied within a wide range. In general, however, you will work between 0 and 150 ° C, preferably between 20 and 110 ° C.

Arbeitet man nach Verfahrensvariante b), so wird in der ersten Stufe das 5-Hydroxy-indan der Formel (II) zweckmäßigerweise in Gegenwart inerter Lösungsmittel, wie aromatische, gegebenenfalls chlorierte, Kohlenwasserstoffe, so z.B. Benzol, Toluol, Xylol oder Chlorbenzol, mit einem Überschuß an Phosgen in den Chlorkohlensäureester überführt. Die entstehende Salzsäure wird durch Zutropfen einer Base, zweckmäßigerweise Natriumhydroxid, gebunden und so der pH-Wert der Reaktionslösung unter 7 gehalten. Im allgemeinen wird man bei einer Reaktionstemperatur zwischen -20 und +20°C, vorzugsweise zwischen -10 und +10°C, arbeiten. In der zweiten Stufe wird der Chlorkohlensäureester entweder nach Isolierung oder aber direkt in der erhaltenen Reaktionslösung mit der äquivalenten Menge Alkylamin umgesetzt. Dabei arbeitet man ebenfalls zweckmäßigerweise in Gegenwart von inerten Lösungsmitteln wie aromatischen und aliphatischen, gegebenenfalls chlorierten Kohlenwasserstoffen, wie Benzol, Toluol, Chlorbenzol, Benzin, Tetrachlorkohlenstoff, oder Äthern, wie Dioxan. Die Reaktionstemperaturen können wiederum in einem gewissen Bereich variiert werden; man arbeitet im allgemeinen zwischen -20 und +20°C, vorzugsweise zwischen -10 und +10°C.If you work according to process variant b), in the first stage the 5-hydroxy-indane of the formula (II) is advantageously in the presence of inert solvents, such as aromatic, optionally chlorinated, hydrocarbons, e.g. Benzene, toluene, xylene or chlorobenzene, with an excess of phosgene in the chlorocarbonic acid ester. The hydrochloric acid formed is bound by dropwise addition of a base, advantageously sodium hydroxide, and the pH of the reaction solution is thus kept below 7. In general, you will work at a reaction temperature between -20 and + 20 ° C, preferably between -10 and + 10 ° C. In the second stage, the chlorocarbonic acid ester is reacted with the equivalent amount of alkylamine either after isolation or directly in the reaction solution obtained. It is also convenient to work in the presence of inert solvents such as aromatic and aliphatic, optionally chlorinated hydrocarbons, such as benzene, toluene, chlorobenzene, gasoline, carbon tetrachloride, or ethers, such as dioxane. The reaction temperatures can in turn be varied within a certain range; one generally works between -20 and + 20 ° C, preferably between -10 and + 10 ° C.

Arbeitet man schließlich nach Verfahrensvariante c), so wird in der ersten Stufe das 5-Hydroxy-indan der Formel (11) mit der äquivalenten Menge Phosgen zum Bis-(indanyl)-kohlensäureester umgesetzt. Man führt die Reaktion zweckmäßigerweise in inerten Lösungsmitteln, wie aromatischen Kohlenwasserstoffen, z.B. Benzol und Toluol, durch, wobei man die entstehende Salzsäure durch Zusetzen einer Base, vorzugsseise Alkalihydroxid, bindet. Der pH-Wert der Reaktionslösung sollte etwa bei 8 liegen. Die Reaktionstemperatur kann in einem größeren Bereich variieren, sie liegt im allgemeinen zwischen 0 und 100°C, vorzugsweise zwischen +20 und 60°C.If one finally works according to process variant c), in the first stage the 5-hydroxy in the formula (11) with the equivalent amount of phosgene to the bis (indanyl) carbonic acid ester. The reaction is expediently carried out in inert solvents, such as aromatic hydrocarbons, for example benzene and toluene, the hydrochloric acid formed being bound by adding a base, preferably alkali metal hydroxide. The pH of the reaction solution should be around 8. The reaction temperature can vary within a substantial range, it is generally between 0 and 100 ° C, preferably between +20 and 60 ° C.

Das in der ersten Stufe gebildete Carbonat wird anschließend mit Alkylamin aufgespalten. Dabei arbeitet man zweckmäßigerweise ohne Lösungsmittel. Die Reaktion kann jedoch auch in Lösungsmitteln durchgeführt werden. Die Reaktionstemperaturen liegen zwischen -30 und +40°C, vorzugsweise zwischen -10 und +20°C.The carbonate formed in the first stage is then broken down with alkylamine. It is convenient to work without solvents. However, the reaction can also be carried out in solvents. The reaction temperatures are between -30 and + 40 ° C, preferably between -10 and + 20 ° C.

Die erfindungsgemäßen Wirkstoffe weisen eine starke 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, Basidiomycetes, Deuteromycetes.The active substances according to the invention have a strong 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, Basidiomycetes, Deuteromycetes.

Die erfindungsgemäßen Wirkstoffe haben ein breites Wirkungsspektrum und können angewandt werden gegen parasitäre Pilze, die oberirdische Pflanzenteile befallen oder die Pflanzen vom Boden her angreifen, sowie gegen samenübertragbare Krankheitserreger. Eine besonders gute Wirksamkeit entfalten sie gegen parasitäre Pilze auf oberirdischen Pflanzenteilen.The active compounds according to the invention have a broad spectrum of activity and can be used against parasitic fungi which attack above-ground parts of plants or attack the plants from the ground, and against seed-borne pathogens. They are particularly effective against parasitic fungi on above-ground parts of plants.

Als Pflanzenschutzmittel können die erfindungsgemäßen Wirkstoffe mit besonders gutem Erfolg zur Bekämpfung von Venturia-Arten, beispielsweise zur Bekämpfung von Apfelschorf (Fusicladium dendriticum) verwendet werden. Dabei ist zu vermerken, daß die Wirkstoffe nicht nur protektiv, sondern auch kurativ wirksam sind.The active compounds according to the invention can be used with particularly good success as crop protection agents for controlling Venturia species, for example for controlling apple scab (Fusicladium dendriticum). It should be noted that the active ingredients are not only protective, but also curative.

Die Wirkstoffe eignen sich bei guter Pflanzenverträglichkeit und günstiger Warmblütertoxizität zur Bekämpfung von tierischen Schädlingen, insbesondere Insekten, Spinnentieren und Nematoden, die in der Landwirtschaft, in Forsten, im Vorrats- und Materialschutz sowie auf dem Hygienesektor vorkommen. Sie sind gegen normal sensible und resistente Arten sowie gegen alle oder einzelne Entwicklungsstadien wirksam. Zu den oben erwähnten Schädlingen gehören:

  • Aus der Ordnung der Isopoda z.B. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.
  • Aus der Ordnung der Diplopoda z.B. Blaniulus guttulatus.
  • Aus der Ordnung der Chilopoda z.B. Geophilus carpophagus, Scutigera spec.
  • Aus der Ordnung der Symphyla z.B. Scutigerella immaculata.
  • Aus der Ordnung der Thysanura z.B. Lepisma saccharina.
  • Aus der Ordnung der Collembola z.B. Onychiurus armatus.
  • Aus der Ordnung der Orthoptera z.B. Blatta orientalis, Periplaneta americana, Leucophaea maderae,
  • Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides,
  • Melanoplus differentialis, Schistocerca gregaria.
  • Aus der Ordnung der Dermaptera z.B. Forficula auricularia.
  • Aus der Ordnung der Isoptera z.B. Reticulitermes spp..
  • Aus der Ordnung der Anoplura z.B. Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis,
  • Haematopinus spp., Linognathus spp.
With good plant tolerance and favorable toxicity to warm-blooded animals, the active substances are suitable for controlling animal pests, in particular insects, arachnids and nematodes, which occur in agriculture, in forests, in the protection of stored goods and materials, and in the hygiene sector. They are effective against normally sensitive and resistant species as well as against all or individual stages of development. The pests mentioned above include:
  • From the order of the Isopoda, for example Oniscus asellus, Armadillidium vulgare, Porcellio scaber.
  • From the order of the Diplopoda, for example, Blaniulus guttulatus.
  • From the order of the Chilopoda, for example, Geophilus carpophagus and Scutigera spec.
  • From the order of the Symphyla, for example, Scutigerella immaculata.
  • From the order of the Thysanura, for example Lepisma saccharina.
  • From the order of the Collembola, for example Onychiurus armatus.
  • From the order of the Orthoptera, for example Blatta orientalis, Periplaneta americana, Leucophaea maderae,
  • Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides,
  • Melanoplus differentialis, Schistocerca gregaria.
  • From the order of the Dermaptera, for example, Forficula auricularia.
  • From the order of the Isoptera, for example Reticulitermes spp ..
  • From the order of the Anoplura, for example Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis,
  • Haema t opinionus spp., Linognathus spp.

Aus der Ordnung der Mallophaga z.B. Trichodectes spp., Damalinea spp.From the order of the Mallophaga e.g. Trichodectes spp., Damalinea spp.

Aus der Ordnung der Thysanoptera z.B. Hercinothrips femoralis, Thrips tabaci.From the order of the Thysanoptera e.g. Hercinothrips femoralis, Thrips tabaci.

Aus der Ordnung der Heteroptera z.B. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.From the order of the Heteroptera e.g. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.

Aus der Ordnung der Homoptera z.B. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp.From the order of the Homoptera e.g. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Rhoralosobusumumisis, pad. Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp.

Aus der Ordnung der Lepidoptera z.B. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.From the order of the Lepidoptera e.g. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiisisppppi, Fpp., Phyllocnist spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonodanaanaanaanaanaanaanaanaanaa, Capa , Clysia ambiguella, Homona magnanima, Tortrix viridana.

Aus der Ordnung der Coleoptera z.B. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.From the order of the Coleoptera, for example, Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysoisisamamysppas, Atomic spp. , Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus holole, Ptinus holpp. Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.

Aus der Ordnung der Hymenoptera z.B. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.From the order of the Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.

Aus der Ordnung der Diptera z.B. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.From the order of the Diptera e.g. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.

Aus der Ordnung der Siphonaptera z.B. Xenopsylla cheopis, Ceratophyllus spp.From the order of the Siphonaptera e.g. Xenopsylla cheopis, Ceratophyllus spp.

Aus der Ordnung der Arachnida z.B. Scorpio maurus, Latrodectus mactans.From the order of the Arachnida e.g. Scorpio maurus, Latrodectus mactans.

Aus der Ordnung Acarina z.B. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.From the order Acarina e.g. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp.,. Chori ., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.

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 Lösungsmittel als Hilfslösungsmittel verwendet werden. Als flüssige Lösungsmittel kommen in 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, Methyläthylketon, Methytisobutyiketon 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, Quarz, Attapulgit, Montmorillonit oder Diatomeenerde und synthetische Gesteinsmehle, wie hochdisperse Kieselsäure, Aluminiumoxid und Silikate; als Emulgiermittel; nichtionogene und anionische Emulgatoren, wie Polyoxyäthylen-Fettsäure-Ester, Pofyoxyäthylen-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 made in a known manner, e.g. 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, e.g. 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 aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylene or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. Petroleum fractions, alcohols, such as butanol or glycol, and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methytisobutyiketone 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 pressure, e.g. 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, e.g. Alkylaryl polyglycol ether, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; as a dispersant: e.g. Lignin sulfite liquor and methyl cellulose.

Die erfindungsgemäßen Wirkstoffe können in den Formulierungen in Mischung mit anderen bekannten Wirkstoffen vorliegen, wie Fungiziden, Insektiziden, Akariziden, Nematiziden, Herbiziden, Schutzstoffen gegen Vogelfraß, Wuchsstoffen, Pflanzennährstoffen und Bodenstrukturverbesserungsmitteln.The active compounds according to the invention can be present in the formulations in a mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, herbicides, bird repellants, growth agents, plant nutrients and agents which improve soil structure.

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 durch weiteres Verdünnen bereiteten Anwendungsformen, wie gebrauchsfertige Lösungen, Emulsionen, Suspensionen, Pulver, Pasten und Granulate angewendet werden. Die Anwendung geschieht in üblicher Weise, z.B. durch Gießen, Spritzen, Sprühen, Stäuben, Streuen, Trockenbeizen, Feuchtbeizen, Naßbeizen, Schlämmbeizen oder Inkrustieren.The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. They are used in the usual way, e.g. by pouring, spraying, spraying, dusting, scattering, dry pickling, wet pickling, wet pickling, slurry pickling or incrusting.

Bei der Verwendung als Blattfungizide können die Wirkstoffkonzentrationen in den Anwendungsformen in einem größeren Bereich variiert werden. Sie liegen im allgemeinen zwischen 0,1 und 0,00001 Gewichtsprozenten, vorzugsweise zwischen 0,05 und 0,0001 %.When used as leaf fungicides, the active compound concentrations in the use forms can be varied within a substantial range. They are generally between 0.1 and 0.00001 percent by weight, preferably between 0.05 and 0.0001%.

Bei der Saatgutbehandlung werden im allgemeinen Wirkstoffmengen von 0,001 bis 50 g je Kilogramm Saatgut, vorzugsweise 0,01 bis 10 g benötigt.In the case of seed treatment, amounts of active ingredient of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required.

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

In weiter unten beschriebenen Versuchen wird die Arthropodenentwicklungshemmende Wirkung der erfindungsgemäßen Verbindungen aufgezeigt. Dabei werden während der gesamten angegebenen Entwicklung der Testtiere die morphologischen Veränderungen, wie zur Hälfte verpuppte Tiere, unvollständig geschlüpfte Larven oder Raupen, defekte Flügel, pupale Kutikula bei Imagines etc., als Mißbildungen gewertet. Die Summe der morphologischen Mißbildungen, zusammen mit den während des Häutungsgeschehens oder der Metamorphose abgetöteten Tiere, wird in Prozent der Versuchstiere angegeben.The experiments described below demonstrate the arthropod development-inhibiting activity of the compounds according to the invention. During the entire development of the test animals, the morphological changes, such as half pupated animals, incompletely hatched larvae or caterpillars, defective wings, pupal cuticles in adults, etc., are assessed as malformations. The sum of the morphological malformations, together with the animals killed during the molting process or the metamorphosis, is given in percent of the experimental animals.

Bei höheren Konzentrationen besitzen die erfindungsgemäßen Verbindungen auch eine insektizide Wirksamkeit.At higher concentrations, the compounds according to the invention also have an insecticidal activity.

Die vielseitigen Anwendungsmöglichkeiten der erfindungsgemäßen Wirkstoffe gehen aus den nachfolgenden Verwendungsbeispielen hervor:The various possible uses of the active compounds according to the invention can be seen from the examples below:

Beispiel AExample A Fusicladium-Test (Apfel)/ProtektivFusicladium test (apple) / protective Lösungsmittel: 4,7 Gew.-Teile AcetonSolvent: 4.7 parts by weight of acetone Emulgator: 0,3 Gew.-Teile Alkyl-aryl-polyglykolätherEmulsifier: 0.3 part by weight of alkyl aryl polyglycol ether Wasser: 95 Gew. TeileWater: 95 parts by weight

Man vermischt die für die gewünschte Wirkstoffkonzentration in der Spritzflüssigkeit nötige Wirkstoffmenge mit der angegebenen Menge des Lösungsmittels und verdünnt das Konzentrat mit der angegebenen Menge Wasser, welches die genannten Zusätze enthält.The amount of active ingredient required for the desired active ingredient concentration in the spray liquid is mixed with the stated amount of solvent and the concentrate is diluted with the stated amount of water which contains the additives mentioned.

Mit der Spritzflüssigkeit bespritzt man junge Apfelsämlinge, die sich im 4- bis 6-Blattstadium befinden, bis zur Tropfnässe. Die Pflanzen verbleiben 24 Stunden bei 20°C und einer relativen Luftfeuchtigkeit von 70% im Gewächshaus. Anschließend werden sie mit einer wäßrigen Konidiensuspension des Apfelschorferregers (Fusicladium dendriticum) inokuliert und 18 Stunden lang in einer Feuchtkammer bei 18 bis 20°C und 10096 relativer Luftfeuchtigkeit inkubiert.The spray liquid is used to spray young apple seedlings, which are in the 4- to 6-leaf stage, until they drip wet. The plants remain in the greenhouse for 24 hours at 20 ° C. and a relative humidity of 70%. They are then inoculated with an aqueous conidia suspension of the apple scab pathogen (Fusicladium dendriticum) and incubated for 18 hours in a humid chamber at 18 to 20 ° C. and 10096 relative atmospheric humidity.

Die Pflanzen kommen dann erneut für 14 Tage ins Gewächshaus.The plants then return to the greenhouse for 14 days.

15 Tage nach der Inokulation wird der Befall der Sämlinge bestimmt. Die erhaltenen Boniturwerte werden in Prozent Befall umgerechnet. 0% bedeutet keinen Befall, 100% bedeutet, daß die Pflanzen vollständig befallen sind.The infestation of the seedlings is determined 15 days after the inoculation. The rating values received are converted into percent infestation. 0% means no infection, 100% means that the plants are completely infected.

Die erfindungsgemäßen Verbindungen entsprechend den Herstellungsbeispielen 1 und 2 zeigen dabei eine gute, dem beim Stand der Technik aufgegebenen Vergleichspräparat überlegene Wirkung.The compounds according to the invention corresponding to preparation examples 1 and 2 show a good action which is superior to the comparative preparation given in the prior art.

Beispiel BExample B Fusicladium-Test (Apfel)/KurativFusicladium test (apple) / curative Lösungsmittel: 4,7 Gew.-Teile AcetonSolvent: 4.7 parts by weight of acetone Emulgator: 0,3 Gew.-Teile Alkyl-aryl-polyglykolätherEmulsifier: 0.3 part by weight of alkyl aryl polyglycol ether Wasser: 95 Gew.-TeileWater: 95 parts by weight

Man vermischt die für die gewünschte Wirkstoffkonzentration in der Spritzflüssigkeit nötige Wirkstoffmenge mit der angegebenen Menge des Lösungsmittels und verdünnt das Konzentrat mit der angegebenen Menge Wasser, welches die genannten Zusätze enthält.The amount of active ingredient required for the desired active ingredient concentration in the spray liquid is mixed with the stated amount of solvent and the concentrate is diluted with the stated amount of water which contains the additives mentioned.

Junge Apfelsämlinge, die sich im 4- bis 6-Blattstadium befinden, werden mit einer wäßrigen Konidiensuspension des Apfelschorferregers (Fusicladium dentriticum) inokuliert und 18 Stunden lang in einer Feuchtkammer bei 18 bis 20°C und 100% relativer Luftfeuchtigkeit inkubiert. Die Pflanzen kommen anschließend ins-Gewächshaus. Sie trocknen ab.Young apple seedlings, which are in the 4 to 6 leaf stage, are inoculated with an aqueous conidia suspension of the apple scab pathogen (Fusicladium dentriticum) and incubated for 18 hours in a humid chamber at 18 to 20 ° C. and 100% relative atmospheric humidity. The plants then come into the greenhouse. They dry up.

Nach einer angemesenen Verweilzeit werden die Pflanzen mit der Spritzflüssigkeit, die in der oben angegebenen Weise hergestellt wirde, bis zur Tropfnässe bespritzt. Anschließend kommen die Pflanzen erneut ins Gewächshaus.After a reasonable dwell time, the plants are sprayed with the spray liquid, which is produced in the manner described above, to the point of dripping wet. Then the plants come back into the greenhouse.

15 Tage nach der Inokulation wird der Befall der Apfelsämlinge bestimmt. Die erhaltenen Boniturwerte werden in Prozent Befall umgerechnet. 0% bedeutet keinen Befall, 100% bedeutet, daß die Pflanzen vollständig befallen sind.The infestation of the apple seedlings is determined 15 days after the inoculation. The rating values received are converted into percent infestation. 0% means no infection, 100% means that the plants are completely infected.

Die erfindungsgemäße Verbindung entsprechend dem Herstellungsbeispiel 1 zeigt dabei eine gute, dem beim Stand der Technik angegebenen Vergleichspräparat überlegene Wirkung.The compound according to the invention corresponding to preparation example 1 shows a good effect which is superior to the comparative preparation given in the prior art.

Beispiel CExample C Entwicklungshemmende Wirkung/FraßtestDevelopmental inhibitory effect / feeding test Testtiere: Plutella maculipennis (Raupen im 4. Entwicklungsstadium) 20 StückTest animals: Plutella maculipennis (caterpillars in the 4th stage of development) 20 pieces

Phaedon cochleariae (Larven im 4. Entwicklungsstadium) 20 Stück

  • Futterpflanzen: Kohlpflanzen (Brassica oleracea)
  • Lösungsmittel: 10 Gew.-Teile Dimethylformamid
  • Emulgator: 1 Gew.-Teil Polyoxyäthylensorbitanmonolaurat
Phaedon cochleariae (4th stage larvae) 20 pieces
  • Forage plants: Cabbage plants (Brassica oleracea)
  • Solvent: 10 parts by weight of dimethylformamide
  • Emulsifier: 1 part by weight of polyoxyethylene sorbitan monolaurate

Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 2 Gew.-Teile Wirksto-f 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 die angegebenen Wirkstoffmengen in ppm (parts pro million) auf den Blättern erhalten werden, bis zur Entwicklung der Imago gefüttert.The test animals are fed leaves of the fodder plants, which are provided with a uniform spray coating of the active compound mixture of the selected concentration, so that the stated amounts of active compound in ppm (parts per million) are 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 erfindungsgemäße Verbindung entsprechend dem Herstellungsbeispiel 1 zeigt dabei gute Wirksamkeit. Sie übertrifft die Wirkung des bekannten Vergleichspräparates 2,2-Dimethyl-6-methoxy- benzopyran.The compound according to the invention according to Preparation Example 1 shows good effectiveness. It outperforms the known comparative 2,2-dimethyl-6-methoxy-benzopyran.

Beispiel DExample D Entwicklungshemmende WirkungDevelopment-inhibiting effect Testtier: Ceratitis capitata (Eier) 20 StückTest animal: Ceratitis capitata (eggs) 20 pieces Futter: Kunstfutter (Möhrenpulver mit Hefepulver)Lining: synthetic lining (carrot powder with yeast powder) Lösungsmittel: 20 Gew.-Teile AcetonSolvent: 20 parts by weight of acetone Emulgator: 5 Gew.-Teile AlkylarylpolyglykolätherEmulsifier: 5 parts by weight of alkylaryl polyglycol ether

Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 4 Gew.-Teile 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, 4 parts by weight of active compound are mixed with the stated amount of solvent, emulsifier and enough water to produce a 1% mixture which is diluted with water to the desired concentration.

Die Eier der Testtiere werden auf eine Schale mit Kunstfutter gebracht, in das die gewählte Konzentration der Wirkstoffmischung eingearbeitet ist, so daß die angegebene Wirkstoffmenge in ppm (parts pro million) erreicht wird. Es wird die Entwicklung bis zum Schlupf der Fliegen beobachtet.The eggs of the test animals are placed on a bowl of artificial feed into which the selected concentration of the active ingredient mixture is incorporated, so that the specified amount of active ingredient in ppm (parts per million) is reached. The development up to the hatching of the flies is observed.

Zur Kontrolle wird nur mit Lösungsmittel und Emulgator der angegebenen Konzentration vermischtes Kunstfutter angeboten.As a control, only synthetic feed mixed with solvent and emulsifier of the specified concentration is offered.

Die erfindungsgemäßen Wirkstoffe entsprechend der Herstellungsbeispiele zeigen dabei gute Wirksamkeit.The active compounds according to the preparation examples according to the invention show good activity.

HerstellungsbeispieleManufacturing examples Beispiel 1example 1

Figure imgb0008
Figure imgb0008

50 g (ca. 0,26 Mol) 5-Hydroxy-3,3,6,7-tetramethyl-indan werden bei Raumtemperatur in 300 ml Ligroin gelöst und mit 20 Tropfen Triäthylamin und 30 g (ca. 0,53 Mol) Methylisocyanat versetzt. Nach dreistündigem Kochen unter Rückfluß läßt man abkühlen. Die Reaktionslösung wird auf Eis gegeben. Die hierbei ausgefallenen Kristalle werden abgesaugt und aus Toluol umkristallisiert. Die Ausbeute beträgt 52,5 g 3,3,6,7-Tetramethylindan-5-yl- N-methyl -carbaminsäureester vom Fp. 148,5-150°C. Vorprodukt:50 g (approx. 0.26 mol) of 5-hydroxy-3,3,6,7-tetramethyl-indan are dissolved in 300 ml of ligroin at room temperature and with 20 drops of triethylamine and 30 g (approx. 0.53 mol) of methyl isocyanate transferred. After boiling under reflux for three hours, the mixture is allowed to cool. The reaction solution is poured onto ice. The crystals which precipitate out are filtered off with suction and recrystallized from toluene. The yield is 52.5 g of 3,3,6,7-tetramethylindan-5-yl-N-methyl-carbamic acid ester, mp. 148.5-150 ° C. Preliminary product:

Das für obige Synthese benötigte 5-Hydroxy-3,3,6,7-tetramethyl-indan wird wie folgt hergestellt:The 5-hydroxy-3,3,6,7-tetramethyl-indane required for the above synthesis is prepared as follows:

Zu einer Lösung von 732 g 2,3-Dimethyl-phenol, 76,5 g 85%iger Phosphorsäure und 6 ml Wasser in 1,44 I o-Dichlor-benzol werden bei 150°C innerhalb von 7 Stunden 449 g Isopren, das mit 1-,3 g Phenothiazin stabilisiert ist, zugetropft. Zur Vervollständigung der Reaktion läßt man über Nacht bei 150°C nachrühren. Die Säurephase wird abgetrennt, und die organische Phase wäscht man neutral. Die fraktionierende Destillation ergibt 526 g 5-Hydroxy-3,3,6,7-tetramethyl-indan; Kp,5: 165-167°C; Fp: 117-118°C.To a solution of 732 g of 2,3-dimethyl-phenol, 76.5 g of 85% phosphoric acid and 6 ml of water in 1.44 l of o-dichlorobenzene are 449 g of isoprene at 150 ° C within 7 hours is stabilized with 1-3 g of phenothiazine, added dropwise. To complete the reaction, the mixture is stirred at 150 ° C. overnight. The acid phase is separated off and the organic phase is washed neutral. Fractional distillation gives 526 g of 5-hydroxy-3,3,6,7-tetramethyl-indane; Bp 5 : 165-167 ° C; Mp: 117-118 ° C.

Beispiel 2Example 2

Figure imgb0009
Figure imgb0009

40 g (0,19 Mol) 7-Chlor-5-hydroxy-3,3,6,7-trimethyl-indan werden bei Raumtemperatur in 200 ml Ligroin gelöst und mit 15 Tropfen Triäthylamin und 21,7 g (0,38 Mol) Methylisocyanat versetzt. Nach 24-stündigem Kochen unter Rückfluß läßt man abkühlen. Zur Reaktionslösung werden 400 ml Wasser gegeben. Die hierbei ausgefallenen Kristalle werden abgesaugt, mit Wasser gewaschen, getrocknet und aus Toluol umkristallisiert. Die Ausbeute beträgt 40 g 3,3,6-Trimethyl-7-chlorindan-6-yl-N-methyl -carbaminsäureester vom Fp: 146―146,5°C.40 g (0.19 mol) of 7-chloro-5-hydroxy-3,3,6,7-trimethyl-indan are dissolved in 200 ml of ligroin at room temperature and mixed with 15 drops of triethylamine and 21.7 g (0.38 mol ) Added methyl isocyanate. After boiling under reflux for 24 hours, the mixture is allowed to cool. 400 ml of water are added to the reaction solution. The crystals which precipitate out are filtered off with suction, washed with water, dried and recrystallized from toluene. The yield is 40 g of 3,3,6-trimethyl-7-chloroindan-6-yl-N-methyl-carbamic acid ester, mp: 146-146.5 ° C.

Vorprodukt:Preliminary product:

Das für obige Synthese benötigte 7-Chlor-5-hydroxy-3,3,6-trimethyl-indan wird wie folgt hergestellt:The 7-chloro-5-hydroxy-3,3,6-trimethyl-indane required for the above synthesis is prepared as follows:

Zu einer Lösung von 832 g 3-Chlor-2-methyl-phenol, 74,4 g 85%iger Phosphorsäure und 5,8 ml Wasser in 1,4 1 o-Dichtor-benzol werden bei 110°C innerhalb von 6 Stunden 437 g lsopren, das mit 1,3 g Phenothiazin stabilisiert ist, zugetropft Zur Vervollständigung der Reaktion läßt man über Nacht bei 110°C nachrühren. Die Säurephase wird abgetrennt, und die organische Phase wäscht man neutral. Die fraktionierende Destillation ergibt 296 g 7-Chlor-5-hydroxy-3,3,6-trimethylindan; Kp11: 161-164°C; Fp: 109-109,5°C.A solution of 832 g of 3-chloro-2-methylphenol, 74.4 g of 85% phosphoric acid and 5.8 ml of water in 1.4 l of o-dichloro-benzene are 437 at 110 ° C within 6 hours g of isoprene, which is stabilized with 1.3 g of phenothiazine, added dropwise. To complete the reaction, the mixture is stirred at 110 ° C. overnight. The acid phase is separated off and the organic phase is washed neutral. Fractional distillation gives 296 g of 7-chloro-5-hydroxy-3,3,6-trimethylindane; Bp 11 : 161-164 ° C; Mp: 109-109.5 ° C.

In ähnlicher Weise, wie in obligen Beispielen beschrieben, werden die folgenden Verbindungen der allgemeinen Formel

Figure imgb0010
erhalten:
Figure imgb0011
 In a similar manner, as described in the examples given, the following compounds of the general formula
Figure imgb0010
 receive:
Figure imgb0011

Claims (4)

1. lndan-5-yl N-alkyl-carbamic acid esters of the general formula
Figure imgb0014
in which
R' represents alkyl,
R2 represents hydrogen or alkyl and
R3 and R4 represent chlorine or alkyl.
2. A process for the preparation of indan-5-yl N-alkyl-carbamic acid esters characterised in that
a) 5-hydroxy-indans of the formula
Figure imgb0015
in which
R2, R3 and R4 have the meaning stated above, are reacted with an alkyl isocyanate, or
b) 5-hydroxy-indans of the formula (II) are converted, in a first step, to the corresponding chloro- carbonic acid ester by means of an excess of phosgene, and this ester is reacted with alkylamine, or
c) 5-hydroxy-indans of the formula (11) are reacted, in a first step, with the equivalent amount of phosgene to give the corresponding bis-indanyl carbonate, and this is split, in a second step, with alkylamine.
3. A fungicidal or arthropod development-inhibiting composition characterised by a content of at least one indan-5-yl N-alkyl-carbamic acid ester according to Claim 1.
4. The use of indan-5-yl N-alkyl-carbamic acid esters according to Claim 1 for combating fungi and for inhibiting the development of arthropods.
EP78100703A 1977-08-31 1978-08-18 5-indanyl esters of n-alkyl carbamic acid, processes for their preparation and their use as pesticides Expired EP0000934B1 (en)

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DE19772739193 DE2739193A1 (en) 1977-08-31 1977-08-31 INDAN-5-YL-N-ALKYL-CARBAMIC ACID ESTER, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS A PLANT PROTECTANT

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