EP0662963A1 - Naphthol derivatives, a method for producing the same and their use as herbicides - Google Patents

Naphthol derivatives, a method for producing the same and their use as herbicides

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Publication number
EP0662963A1
EP0662963A1 EP93919629A EP93919629A EP0662963A1 EP 0662963 A1 EP0662963 A1 EP 0662963A1 EP 93919629 A EP93919629 A EP 93919629A EP 93919629 A EP93919629 A EP 93919629A EP 0662963 A1 EP0662963 A1 EP 0662963A1
Authority
EP
European Patent Office
Prior art keywords
group
groups
naphthol derivative
alkyl
atom
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP93919629A
Other languages
German (de)
French (fr)
Inventor
Mitsunori Hiratsuka
Toru Uekawa
Naonori Hirata
Kazuo Saito
Hiroyuki Yogai
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Filing date
Publication date
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Publication of EP0662963A1 publication Critical patent/EP0662963A1/en
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/34—One oxygen atom
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C239/00—Compounds containing nitrogen-to-halogen bonds; Hydroxylamino compounds or ethers or esters thereof
    • C07C239/08—Hydroxylamino compounds or their ethers or esters
    • C07C239/22—Hydroxylamino compounds or their ethers or esters having oxygen atoms of hydroxylamino groups esterified
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or 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 to ring carbon atoms
    • C07D215/48—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/52—Two oxygen atoms
    • C07D239/54—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals
    • C07D239/545—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals with other hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/553—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals with other hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms with halogen atoms or nitro radicals directly attached to ring carbon atoms, e.g. fluorouracil
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/60—Three or more oxygen or sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/30—Only oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • NAPHTHOL DERIVATIVES A METHOD FOR PRODUCING THE SAME AND THEIR USE AS HERBICIDES
  • the present invention relates to novel naphthol derivatives, a method for producing the same and their use as herbicides.
  • naphthol derivatives represented by the following formula (I) are excellent compounds as herbicides which can control weeds widely generated in crop lands or non-crop lands at low dosage rate, have a broad herbicidal spectrum and also can safely be used for no-till cultivation.
  • the present invention is based on this finding.
  • the present invention provides naphthol derivatives represented by the formula (T) [hereinafter referred to as the present compound(s) ] , a method for producing the same and their use as herbicides:
  • X represents CH or a nitrogen atom
  • Z represents CH or a nitrogen atom
  • W represents an oxygen atom or a sulfur atom; each of Y 1 , Y 2 and Y3 which may be the same or different, represents a hydrogen atom, a C ⁇ -C 6 alkyl group, a halogen atom or a Ci-C ⁇ , alkoxy group.
  • each of R3 and R 4 which may be the same or different, is preferably a Ci-C ⁇ alkoxy, and more preferably both of R3 and R 4 are methoxy groups.
  • W is preferably an oxygen atom.
  • examples of the Ci-C ⁇ alkyl groups and alkyl moiety of the haloalkyl groups include methyl, ethyl, n-propyl, i- propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl groups and the like;
  • examples of the Ci-C ⁇ alkoxy groups and alkoxy moiety of the C ⁇ C 6 alkoxycarbonyl groups include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, n- hexyloxy groups and the like;
  • examples of the C 3 -C 6 cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl groups and the like;
  • examples of the halogen atom and halogen moiety of the halo-Ci-C ⁇ alkyl groups include fluorine, chlorine and bromine; examples of
  • benzyl group optionally substituted with at least one member selected from the group consisting of Ci-C ⁇ alkyl groups, halogen atoms, Ci-C ⁇ alkoxy groups, halo-Ci-C ⁇ alkyl groups, nitro groups, cyano groups and Ci-C ⁇ alkoxycarbonyl groups include benzyl, 2-methylbenzyl, 3-ethylbenzyl, 4- hexylbenzyl, 2,6-dimethylbenzyl, 2-fluorobenzyl, 2- chlorobenzyl, 3-bromobenzy
  • a method for producing the present compound is as follows:
  • the present compound (I) can be produced by reacting a naphthol derivative represented by the formula (II) ,
  • This reaction is usually carried out with or without a solvent in the presence of a base.
  • the reaction temperature usually ranges from room temperature to the boiling point of the solvent, and the reaction time ranges from 1 hour to 24 hours.
  • the amount of the compound (III) is 1 to 3 equivalents based on 1 equivalent of the naphthol derivative (II), and that of the base is 1 to 5 equivalents based on the same.
  • the solvent includes aliphatic hydrocarbons (e.g. hexane, heptane, ligroin, petroleum ether), aromatic hydrocarbons (e.g. benzene, toluene, xylene), halogenated hydrocabons (e.g.
  • ethers e.g. diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether
  • ketones e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone
  • esters e.g. ethyl formate, ethyl acetate, butyl acetate, diethyl carbonate
  • nitro compounds e.g.
  • nitroethane, nitrobenzene nitriles (e.g. acetonitrile, isobutyronitrile), tertiary amines (e.g. pyridine, triethylamine, N,N-diethylaniline, tributylamine, N-methylmorpholine) , acid amides (e.g. formamide, N,N-dimethylformamide, acetamine), sulfur compounds (e.g. dimethyl sulfoxide, sulfolane), water and mixtures thereof.
  • nitriles e.g. acetonitrile, isobutyronitrile
  • tertiary amines e.g. pyridine, triethylamine, N,N-diethylaniline, tributylamine, N-methylmorpholine
  • acid amides e.g. formamide, N,N-dimethylformamide, acetamine
  • sulfur compounds e.g
  • the base includes inorganic bases (e.g. sodium carbonate, potassium carbonate, sodium hydride), etc.
  • inorganic bases e.g. sodium carbonate, potassium carbonate, sodium hydride
  • reaction solution After completion of the reaction, the reaction solution is after-treated as usual. That is, water is added to the solution which is then extracted with an organic solvent and concentrated, and if necessary, the product obtained is subjected to chromatography, distillation, recrystallization, etc. Thus, the desired present compound can be obtained.
  • the present compound (I) can also be produced by reacting [reaction (i)] the compound (IV)
  • the acid- halogenating agent includes thionyl chloride, thionyl bromide, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, phosphorus oxychloride, phosgene, oxalyl chloride, etc.
  • the active esterifying agent includes N,N'-disubstituted carbodiimides such as N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodi- imide, l-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, etc.; arylsulfonyl chlorides such as 2,4,6-trimethylbenzenesulfonyl chloride, 2,4,6- triisopropylbenzenesulfonyl chloride, etc.; N,N'- carbonyldiimidazole; diphenylphosphorylazide; N- ethoxycarbonyl-2-ethoxy-l,2-dihydroquinoline; N-ethyl- 2'-hydroxybenzisoxazolium tetrafluoroborate; N-ethyl-5- phenylisoxazolium-3 '-s
  • R3, R 4 , X, ⁇ i, Y , ⁇ 3, z and W are as defined above, is produced in the reaction system.
  • the substituent W2 represents a halogen atom when the acid-halogenating agent was used;
  • W 2 represents an N,N'-disubstituted-2- isoureide group when N,N'-disubstituted carbodiimide was used as the active esterifying agent;
  • W2 represents an arylsulfonyloxy group when arylsulfonyl chloride was used as said agent;
  • W 2 represents an imidazolyl group when N,N'-carbonyldiimidazole was used as said agent;
  • 2 represents an azide group when diphenylphosphorylazide was used as said agent;
  • 2 represents an ethoxycarbonyl- oxy group when N-ethoxycarbonyl-2-ethoxy-l,2-dihydro- quinoline was used as said agent;
  • W 2 represents 3-(N- ethylaminocarbonyl)-2-hydroxyphenoxy group when N-ethyl- 2'-
  • reaction system 2 can also take a form of an acid anhydride represented by the formula,
  • the amount of the foregoing acid-halogenating agent or active esterifying agent used is usually 1 to 10 equivalents based on 1 equivalent of the compound (IV).
  • the amount of the compound of the formula (V) used is usually 1 to 5 equivalents based on 1 equivalent of the compound (IV).
  • the reactions (i) and (ii) can also be carried out, if necessary, in the presence of a base.
  • a base includes organic bases (e.g. 1-methylimidazole, 3- nitro-lH-l,2,4-triazole, lH-tetrazole, 1H-1,2,4- triazole, imidazole, pyridine, triethylamine) and inorganic bases (e.g. potassium carbonate).
  • the amount of the base used is 1 to 20 equivalents based on 1 equivalent of the compound (IV).
  • the reactions (i) and (ii) are usually carried out in the presence of an inert solvent.
  • a solvent includes aliphatic hydrocarbons (e.g. hexane, heptane, ligroin, petroleum ether), aromatic hydrocarbons (e.g. benzene, toluene, xylene), halogenated hydrocarbons
  • ethers e.g. diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether
  • ketones e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone
  • esters e.g. ethyl formate, ethyl acetate, butyl acetate
  • nitro compounds e.g.
  • nitroethane, nitrobenzene nitriles (e.g. acetonitrile, isobutyronitrile), tertiary amines (e.g. pyridine, triethylamine, N,N-diethylaniline, tributylamine, N- methylmorpholine) , acid amides (e.g. N,N-dirnethyl- formamide), sulfur compounds (e.g. dimethyl sulfoxide, sulfolane) and mixtures thereof.
  • the reaction temperature ranges from 0°C to the boiling point of the solvent in any of the reactions (i) and (ii).
  • the reaction time ranges from 1 to 24 hours for each reaction, and from about 1 to about 48 hours for the reactions (i) through (ii).
  • the reaction solution is after-treated as usual. That is, water is added to the solution which is then extracted with an organic solvent and concentrated, and if necessary, the product obtained is subjected to chromatography, distillation, recrystallization, etc. Thus, the desired present compound can be obtained.
  • the present compounds (I) include their stereoisomers having a herbicidal activity.
  • the compound represented by the formula (II) can be produced by reacting a compound represented by the formula (VII) ,
  • reaction (iii) an acid-halogenating agent or an active esterifying agent
  • reaction (iv) reacting the resulting reaction product with the compound represented by the formula (V) (hereinafter reaction (iv)).
  • the above reactions (iii) and (iv) can be carried out according to the foregoing reactions (i) and (ii), respectively.
  • the compound (VII) can be produced according to
  • the compound represented by the formula (IV) can be produced by reacting the compound (VII) with the compound (III) according to the foregoing reaction (A).
  • the present compounds (I) have an excellent herbicidal activity and some of them have excellent selectivity between crops and weeds.
  • the present compounds when used for foliar treatment and soil treatment in upland fields, ridge or no-cultivating area, exhibit a herbicidal activity against various weeds, such as, Polygonaceae wild buckwheat (Polyqonum convolvulus) , pale smartweed (Polyqonum lapathifolium) , Pennsylvania smartweed (Polyqonum pensylvanicum) , ladysthumb (Polyqonum persicaria) , curly dock (Rumex crispus) , broadleaf dock (Rumex obtusifolius) Portulacaceae common purslane (Portulaca oleracea) Caryophyllaceae common chickweed (Stellaria media) Chenopodiaceae common lambsquarters (Chenopodium album) , kochia (Kochia scoparia) Amaranthaceae redroot pigweed (Amaranthus retroflexus) , smooth pigweed (
  • inteqriuscula pitted morningglory (Ipomoea lacunosa) , field bingweed (Convolvulus arvensis) Labiatae red deadnettle (Lamiu purpureum) , henbit (Lamium amplexicaule) Solanaceae jimsonweed (Datula stramonium) , black nightshade (Solanum niqram) Scrophulariaceae birdseye speedwell (Veronica persica) , ivyleaf speedwell (Veronica hederaefolia) Compositae common cocklebur (Xanthium pensylvanicu ) , common sunflower (Helianthus annuus) , scentless chamomile (Matricaria inodora) , corn marigold
  • some of the present compounds give such no phytotoxicity as becoming a problem to main crops such as corn (Zea mays) , wheat (Triticum aestivum) , barley (Hordeum vulqare) , rice (Oryza sativa) , soybean (Glycine max) , cotton (Gossypium spp) , sugar beet (Beta vulqaris) , peanut (Arachis hypoqaea) , sunflower (Helianthus annuus) , rape (Brassica napus) , etc. and horticultural crops such as flower, ornamental plants and vegetables.
  • the present compound (I) also can safely be used for no-till cultivation in soybean fields, peanut fields, corn fields, etc., and some of them give such no phytotoxicity as becoming a problem to crops.
  • the present compounds exhibit a herbicidal activity against weeds such as Gramineae
  • the present compound (I) can be used as an active ingredient for herbicides used in orchards, pastures, turfs, forests, afforestation area and non- agricultural fields (e.g. water way, canal), etc.
  • the present compound (I) When used as an active ingredient for herbicides, it is usually formulated before use into emulsifiable concentrates, wettable powders, suspension formulations, granules, water-dispersible granules, etc. by mixing with solid carriers, liquid carriers, surface active agents or other auxiliaries for formulation.
  • the content of the compound (I) as an active ingredient in these preparations is normally within a range of about 0.003 to 90% by weight, preferably of about 0.01 to 80% by weight.
  • solid carriers examples include fine powders or granules of kaolin clay, attapulgite clay, bentonite, terra alba, pyrophyllite, talc, diatomaceous earth, calcite, walnut shell powders, urea, ammonium sulfate, synthetic hydrated silicon dioxide, etc.
  • liquid carriers examples include aromatic hydrocarbons (e.g. xylene, alkylbenzene, methyl- naphthalene, phenylquinolylethane) , alcohols (e.g. isopropanol, ethylene glycol), esters (e.g. dialkyl phthalate), ketones (e.g. acetone, cyclohexanone, isophorone), mineral oils (e.g. machine oil), vegetable oils (e.g. soybean oil, cotton seed oil), dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, N- methylpyrrolidone, water, etc.
  • aromatic hydrocarbons e.g. xylene, alkylbenzene, methyl- naphthalene, phenylquinolylethane
  • alcohols e.g. isopropanol, ethylene glycol
  • esters e.g. dialkyl phthalate
  • ketones e.g.
  • Examples of the surface active agents used for emulsification, dispersion, spreading, etc. are anionic surface active agents such as salts of alkyl sulfates, alkylsulfonates, alkylarylsulfonates, dialkyl sulfosuccinates, salts of polyoxyethylene alkylaryl ether phosphoric acid esters, etc., and nonionic surface active agents such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, etc.
  • Examples of other auxiliary agents for formulation are lignosulfonates, alginates, polyvinyl alcohol, gum arabic, CMC (carboxymethyl cellulose), PAP (isopropyl acid phosphate), etc.
  • the present compound (I) is usually formulated and used in soil treatment, foliar treatment or flooding treatment before or after emergence of weeds.
  • the soil treatment includes soil surface treatment, soil incorpo ⁇ ration treatment, etc.
  • the foliar treatment includes, in addition to treatment of plants from above, directed treatment in which treatment is limited to weeds only so as not to adhere to crops.
  • the present compound (I) can be used in mixture with other herbicides. Further, the present compound (I) can also be used in mixture with insecticides, acaricides, nematocides, fungicides, bacteriocides, plant growth regulators, fertilizers, soil improvers, etc.
  • insecticides acaricides, nematocides, fungicides, bacteriocides, plant growth regulators, fertilizers, soil improvers, etc.
  • their dosage rate varies with weather conditions, preparation forms, when, how and where the treatment is carried out, weeds species to be controlled, crops species to be protected, etc. Usually, however, the dosage rate is from 1 gram to 10000 grams of the active ingredient per hectare, preferably from 3 grams to 5000 grams of the active ingredient per hectare.
  • the herbicidal composition of the present invention formulated into the form of an emulsifiable concentrate, a wettable powder, a suspension formulation or water dispersible granules may ordinarily be employed by diluting it with water at a volume of about 10 to 1000 liters per hectare (if necessary, adjuvants such as a spreading agent are added to the water).
  • adjuvants such as a spreading agent are added to the water.
  • the granules and some suspension formulations are usually applied without being diluted.
  • the adjuvants include, in addition to the foregoing surface active agents, substances such as polyoxyethylene resin acids (esters), lignosulfonates, abietates, dinaphthylmethanedisulfonates and vegetable oils (e.g. crop oil concentrate, soybean oil, corn oil, cotton seed oil, sunflower oil).
  • esters polyoxyethylene resin acids
  • lignosulfonates lignosulfonates
  • abietates e.g. soybean oil concentrate, soybean oil, corn oil, cotton seed oil, sunflower oil.
  • Production Example 2 1.30 Grams of 2- ⁇ (4,6-dimethoxypyrimidine-2- yl)oxy ⁇ -l-naphthoic acid was dissolved in 15 ml of N,N- dimethylformamide and 1.82 g of 2,4,6-triisopropyl- benzenesulfonyl chloride and 0.98 g of 1-methylimidazole were added thereto and stirred for 20 min. at room temperature.
  • N,N-dimethylformamide solution (0.47 g of N,N- dimethylhydroxylamine hydrochloride and 0.58 g of triethylamine dissolved in 5 ml of N,N-dimethyl- formamide) was added thereto and stirred for 1 hour at room temperature.
  • reaction solution was poured into water and extracted with ethyl acetate.
  • organic layer was washed five times saturated sodium chloride solution and dried over anhydrous magnesium sulfate.
  • the solvent was removed under reduced pressure and the residue obtained was subjected to thin-layer chromatography (silica gel, hexane/ethyl acetate 2:1 (v/v)) to obtain 1.20 g of 2- ⁇ (4,6-dimethoxypyrimidine-2-yl)oxy ⁇ -l-(N,N- dimethylaminooxycarbonyl)naphthalene (the present compound (1) ) .
  • 7-hydroxy-8-(N,N- dimethylaminooxycarbonyl)quinoline can be used instead of 2-hydroxy-l-(N,N-dimethylaminooxycarbonyl)naphthalene to obtain 7- ⁇ (4,6-dimethoxy-l,3,5-triazine-2-yl)oxy ⁇ -8- (N,N-dimethylaminooxycarbony1)quinoline.
  • Table 1 illustrates examples of the compound (I) which can be produced by the above procedure of Production Examples.
  • Table 2 illustrates specific examples of the compound (II), which can be produced by using the corresponding starting materials.
  • the herbicidal activity and phytotoxicity were evaluated in eleven stages, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10 by comparing germination and growth of test plants with those untreated. [0]: the states of germination and growth of test plants showed no difference. [10]: test plants either completely died or germination/growth were totally inhibited.
  • Test Example 1 Foliar treatment test in upland field Cylindrical plastic pots of 10 cm in diameter and 10 cm in depth were filled with upland field soil, and the seeds of plants in Table 4 were sowed in the pots and cultivated for 10 days in a greenhouse.
  • test compounds were formulated into emulsifiable concentrates according to Formulation Example 2 and the prescribed amount of each emulsifiable concentrate was diluted with a spreading agent-containing water at a spray volume of 1000 liters/hectare and uniformly applied from above onto the whole foliar portion of the test plants by means of a sprayer. After application, the test plants were cultivated for 19 days in a greenhouse, and the herbicidal activity was examined. The results are shown in Table 4. Table 4
  • Test Example 2 Soil surface treatment test in upland field Cylindrical plastic pots of 10 cm in diameter and 10 cm in depth were filled with upland field soil, and seeds of plants in Table 5 were sowed in the respective pots and covered with soil.
  • the test compounds were formulated into emulsifiable concentrates according to Formulation Example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water at a spray volume of 1000 liters/hectare and uniformly applied onto the whole soil surface by means of a sprayer. After application, the test plants were cultivated for 19 days in a greenhouse, and the herbicidal activity was examined. The results are shown in Table 5. Table 5
  • Vats of 33 x 23 cm 2 in area and 11 cm in depth were filled with upland field soil, and the seeds of the test plant shown in Table 6 were sowed in the respective vats and covered with soil in a thickness of 1 to 2 cm.
  • the test compounds were formulated into emulsifiable concentrates according to Formulation Example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water at a spray volume of 1000 liters/ hectare and uniformly applied onto the whole soil surface by means of a sprayer. After application, the test plants were cultivated for 18 days in a greenhouse, and the herbicidal activity and phytotoxicity were examined. The results are shown in Table 6. Table 6
  • Vats of 33 x 23 cm 2 in area and 11 cm in depth were filled with upland field soil, and seeds of test plants shown in Table 7 were sowed in the respective vats and cultivated for 30 days. Thereafter, the test compounds were formulated into emulsifiable concentrates according to Formulation Example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water at a spray volume of 1000 liters/hectare and uniformly applied from above onto the whole foliar portion of the test plants by means of a sprayer. The conditions of growth of the weed and crops at that time varied depending upon the kind of the test plants, but the test plants were in the 1- to 4-leaf stage and were 2 to 12 cm in height. Eighteen days after application, the herbicidal activity and phytotoxicity were examined. The results are shown in Table 7. This test was carried out in a greenhouse through the whole test period.
  • Vats of 33 x 23 cm 2 in area and 11 cm in depth were filled with upland field soil, and seeds of test plants shown in Table 8 were sowed in the respective vats and cultivated for 16 days. Thereafter, the test compounds were formulated into emulsifiable concentrates according to Formulation Example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water at a spray volume of 1000 liters/hectare and uniformly applied from above onto the whole foliar portion of the test plants by means of a sprayer. The conditions of growth of the weed and crops at that time varied depending upon the kind of the test plants, but the test plants were in the 1- to 4-leaf stage and were 2 to 15 cm in height. Eighteen days after application, the herbicidal activity and phytotoxicity were examined. The results are shown in Table 8. This test was carried out in a greenhouse through the whole test period.
  • Test Example 6 Flooding treatment test in paddy field Wager's pots of 1/5000 ares were filled with paddy field soil, and seeds of test plants shown in Table 9 were sowed and covered with soil in a thickness of 1 to 2 cm. After creating a state of paddy field by water flooding, rice (at the 3-leaf stage) was transplanted and they were cultivated in a greenhouse. After 5 days (at the germination stage of barnyardgrass) , the test compounds were formulated into emulsifiable concentrates according to Formulation Example 2 and the prescribed amount of each of the emulsifiable concentrates was diluted with water and applied onto the water surface in the pots.
  • Vats of 33 x 23 cm 2 in area and 11 cm in depth were filled with upland field soil, and seeds of test plants shown in Table 10 were sowed in the respective vats and cultivated for 30 days. Thereafter, the test compounds were formulated into emulsifiable concentrates according to Formulation Example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water at a spray volume of 1000 liters/hectare and uniformly applied from above onto the whole foliar portion of the test plants by means of a sprayer. The conditions of growth of the weed and crops at that time varied depending upon the kind of the test plants, but the test plants were in the 1- to 4-leaf stage and were 2 to 12 cm in height. Eighteen days after application, the herbicidal activity and phytotoxicity were-e examined. The results are shown in Table 10. This test was carried out in a greenhouse through the whole test period.

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Abstract

Novel naphthol derivatives represented by formula (I), wherein each of R?1 and R2¿, which may be the same or different, represents hydrogen, alkyl, cycloalkyl, or phenyl optionally substituted with at least one member selected from alkyl, halogen, alkoxy, haloalkyl, nitro, cyano and alkoxycarbonyl or benzyl optionally substituted with at least one member selected from alkyl, halogen, alkoxy, haloalkyl, nitro, cyano and alkoxycarbonyl, or R?1 and R2¿ are bonded together at their ends to form alkylene, or R?1 and R2¿ are bonded together at their ends to form alkylene containing an oxygen; each of R?3 and R4¿, which may be the same or different, represents alkyl, alkoxy or halogen; X represents CH or nitrogen; Z represents CH or nitrogen; W represents oxygen or sulfur; each of Y?1, Y2 and Y3¿ which may be the same or different, represents hydrogen, alkyl, halogen or alkoxy; have an excellent herbicidal activity and excellent selectivity to crops with weeds and therefore, can be used as an active ingredient for herbicides.

Description

DESCRIPTION
NAPHTHOL DERIVATIVES, A METHOD FOR PRODUCING THE SAME AND THEIR USE AS HERBICIDES
The present invention relates to novel naphthol derivatives, a method for producing the same and their use as herbicides.
It is well known in the art that certain kinds of compounds can be used as active ingredients for herbicides.
However, these compounds are not always said to be satisfactory because they are insufficient as herbicides. In view of these circumstances, the present inventors have extensively studied, and as a result, have found that naphthol derivatives represented by the following formula (I) are excellent compounds as herbicides which can control weeds widely generated in crop lands or non-crop lands at low dosage rate, have a broad herbicidal spectrum and also can safely be used for no-till cultivation. The present invention is based on this finding.
The present invention provides naphthol derivatives represented by the formula (T) [hereinafter referred to as the present compound(s) ] , a method for producing the same and their use as herbicides:
wherein each of R1 and R2, which may be the same or different, represents a hydrogen atom, a C1-C6 alkyl group, a C3-C6 cycloalkyl group, or a phenyl group optionally substituted with at least one member selected from the group consisting of i-Cξ, alkyl groups, halogen atoms, Ci-Cε alkoxy groups, halo-Cι~C6 alkyl groups, nitro groups, cyano groups and Ci-Ce alkoxycarbonyl groups or a benzyl group optionally substituted with at least one member selected from the group consisting of C1-C6 alkyl groups, halogen atoms, Ci-Cβ alkoxy groups, halo-Ci-Cβ alkyl groups, nitro groups, cyano groups and Ci-Cβ alkoxycarbonyl groups, or Ri and R2 are bonded together at their ends to form a C4-Cβ alkylene group, or Ri and R2 are bonded together at their ends to form a C4-C6 alkylene group containing an oxygen atom; each of R3 and R4, which may be the same or different, represents a Ci-Cε alkyl group, a Ci-Cε alkoxy group or a halogen atom;
X represents CH or a nitrogen atom; Z represents CH or a nitrogen atom;
W represents an oxygen atom or a sulfur atom; each of Y1, Y2 and Y3 which may be the same or different, represents a hydrogen atom, a Cχ-C6 alkyl group, a halogen atom or a Ci-Cς, alkoxy group.
In the compound of the formula (I), each of R3 and R4, which may be the same or different, is preferably a Ci-Cε alkoxy, and more preferably both of R3 and R4 are methoxy groups. W is preferably an oxygen atom.
In the compound of the formula (I), examples of the Ci-Cε alkyl groups and alkyl moiety of the haloalkyl groups include methyl, ethyl, n-propyl, i- propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl groups and the like; examples of the Ci-Cε alkoxy groups and alkoxy moiety of the Cι~C6 alkoxycarbonyl groups include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, n- hexyloxy groups and the like; examples of the C3-C6 cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl groups and the like; examples of the halogen atom and halogen moiety of the halo-Ci-Cβ alkyl groups include fluorine, chlorine and bromine; examples of the halo-Ci-Cε alkyl groups include 2-chloroethyl, 2-bromoethyl, 3-fluoropropyl, 2- chloropropyl, 4-chlorobutyl, 6-chlorohexyl groups and the like; examples of the phenyl group optionally substituted with at least one member selected from the group consisting of Ci-Cβ alkyl groups, halogen atoms, C1-C6 alkoxy groups, halo-Cι-C6 alkyl groups, nitro groups, cyano groups and Ci-Cξ, alkoxycarbonyl groups include phenyl, 2-methylphenyl, 3-ethylphenyl, 4- hexylphenyl, 2,6-dimethylphenyl, 2-fluorophenyl, 2- chlorophenyl, 3-bromophenyl, 2,4-dichlorophenyl, 2- chloro-4-methylphenyl, 3-methoxyphenyl, 3-ethoxyphenyl, 4-i-propoxyphenyl, 3-hexyloxyphenyl, 3-methoxycarbonyl- phenyl, 3-ethoxycarbonylphenyl, 4-i-propoxycarbonyl- phenyl, 3-hexyloxycarbonylphenyl. , 3-nitrophenyl, 4- cyanophenyl, 2-chloromethylphenyl, 2-(2-bromoethyl)- phenyl, 3-(3-fluoropropyl)phenyl, 4-(6-chlorohexyl)- phenyl, 2-(6,6,6-trifluorohexyl)phenyl, 2-dichloro- methylphenyl and the like; examples of the benzyl group optionally substituted with at least one member selected from the group consisting of Ci-Cε alkyl groups, halogen atoms, Ci-Cδ alkoxy groups, halo-Ci-Cβ alkyl groups, nitro groups, cyano groups and Ci-Cδ alkoxycarbonyl groups include benzyl, 2-methylbenzyl, 3-ethylbenzyl, 4- hexylbenzyl, 2,6-dimethylbenzyl, 2-fluorobenzyl, 2- chlorobenzyl, 3-bromobenzyl, 2,4-dichlorobenzyl, 2- chloro-4-methylbenzyl, 3-methoxybenzyl, "3-ethoxybenzyl, 4-i-propoxybenzyl, 3-hexyloxybenzyl, 3-methoxycarbonyl- benzyl, 3-ethoxycarbonylbenzyl, 4-i-propoxycarbonyl- benzyl, 3-hexyloxycarbonylbenzyl, 3-nitrobenzyl, 4- cyanobenzyl, 2-chloromethylbenzyl, 2-(2-bromoethyl)- benzyl, 3-(3-fluoropropyl)benzyl, 4-(6-chlorohexyl)- benzyl, 2-(6,6,6-trifluorohexyl)benzyl, 2-dichloro- methylbenzyl and the like; examples of the C4-C6 alkylene group include tetramethylene, pentamethylene and hexamethylene groups; and examples of the C4-C6 alkylene group having an oxygen atom include -CH2CH2OCH2CH2-, -CH2CH2CH2OCH2CH2-, -CH2CH2CH2CH2OCH2CH2- and the like.
A method for producing the present compound is as follows: The present compound (I) can be produced by reacting a naphthol derivative represented by the formula (II) ,
[wherein Ri, R2, yi. γ2f γ3, and Z are as defined above], with a compound represented by the formula (III),
[wherein X, R3 and R4 are each as defined above and Wi represents a halogen atom, a Ci-Cε alkylsulfonyl group or a benzylsulfonyl group], (reaction (A))
This reaction is usually carried out with or without a solvent in the presence of a base. The reaction temperature usually ranges from room temperature to the boiling point of the solvent, and the reaction time ranges from 1 hour to 24 hours. Referring to the amounts of the reagents used for this reaction, the amount of the compound (III) is 1 to 3 equivalents based on 1 equivalent of the naphthol derivative (II), and that of the base is 1 to 5 equivalents based on the same. The solvent includes aliphatic hydrocarbons (e.g. hexane, heptane, ligroin, petroleum ether), aromatic hydrocarbons (e.g. benzene, toluene, xylene), halogenated hydrocabons (e.g. chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, dichlorobenzene) , ethers (e.g. diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether), ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone) , esters (e.g. ethyl formate, ethyl acetate, butyl acetate, diethyl carbonate), nitro compounds (e.g. nitroethane, nitrobenzene), nitriles (e.g. acetonitrile, isobutyronitrile), tertiary amines (e.g. pyridine, triethylamine, N,N-diethylaniline, tributylamine, N-methylmorpholine) , acid amides (e.g. formamide, N,N-dimethylformamide, acetamine), sulfur compounds (e.g. dimethyl sulfoxide, sulfolane), water and mixtures thereof.
The base includes inorganic bases (e.g. sodium carbonate, potassium carbonate, sodium hydride), etc.
After completion of the reaction, the reaction solution is after-treated as usual. That is, water is added to the solution which is then extracted with an organic solvent and concentrated, and if necessary, the product obtained is subjected to chromatography, distillation, recrystallization, etc. Thus, the desired present compound can be obtained.
The present compound (I) can also be produced by reacting [reaction (i)] the compound (IV)
(wherein R3, R4, x, γi, γ2, γ3, z and w are as defined above) with an acid-halogenating agent or an active esterifying agent, and subsequently reacting [reaction (ii)] the resulting reaction product with an compound represented by the formula (V) , RI
HO-N: (V)
R2
(wherein Ri and R2 are as defined above).
In the above reaction (i), the acid- halogenating agent includes thionyl chloride, thionyl bromide, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, phosphorus oxychloride, phosgene, oxalyl chloride, etc. The active esterifying agent includes N,N'-disubstituted carbodiimides such as N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodi- imide, l-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, etc.; arylsulfonyl chlorides such as 2,4,6-trimethylbenzenesulfonyl chloride, 2,4,6- triisopropylbenzenesulfonyl chloride, etc.; N,N'- carbonyldiimidazole; diphenylphosphorylazide; N- ethoxycarbonyl-2-ethoxy-l,2-dihydroquinoline; N-ethyl- 2'-hydroxybenzisoxazolium tetrafluoroborate; N-ethyl-5- phenylisoxazolium-3 '-sulfonate; etc.
By this reaction, a pyrimidine derivative represented by the formula (VI),
(VI)
wherein R3, R4, X, γi, Y , γ3, z and W are as defined above, is produced in the reaction system.
In the above formula (VI), the substituent W2 represents a halogen atom when the acid-halogenating agent was used; W2 represents an N,N'-disubstituted-2- isoureide group when N,N'-disubstituted carbodiimide was used as the active esterifying agent; W2 represents an arylsulfonyloxy group when arylsulfonyl chloride was used as said agent; W2 represents an imidazolyl group when N,N'-carbonyldiimidazole was used as said agent; 2 represents an azide group when diphenylphosphorylazide was used as said agent; 2 represents an ethoxycarbonyl- oxy group when N-ethoxycarbonyl-2-ethoxy-l,2-dihydro- quinoline was used as said agent; W2 represents 3-(N- ethylaminocarbonyl)-2-hydroxyphenoxy group when N-ethyl- 2'-hydroxybenzisoxazolium tetrafluoroborate was used as said agent; and W2 represents a group
when N-ethyl-5-phenylisoxazolium-3'-sulfonate was used as said agent. In the reaction system, 2 can also take a form of an acid anhydride represented by the formula,
(wherein R3, R4, X, γi, γ2, γ3 z and W are as defined above) .
The amount of the foregoing acid-halogenating agent or active esterifying agent used is usually 1 to 10 equivalents based on 1 equivalent of the compound (IV).
The amount of the compound of the formula (V) used is usually 1 to 5 equivalents based on 1 equivalent of the compound (IV). The reactions (i) and (ii) can also be carried out, if necessary, in the presence of a base. Such a base includes organic bases (e.g. 1-methylimidazole, 3- nitro-lH-l,2,4-triazole, lH-tetrazole, 1H-1,2,4- triazole, imidazole, pyridine, triethylamine) and inorganic bases (e.g. potassium carbonate). The amount of the base used is 1 to 20 equivalents based on 1 equivalent of the compound (IV).
The reactions (i) and (ii) are usually carried out in the presence of an inert solvent. Such a solvent includes aliphatic hydrocarbons (e.g. hexane, heptane, ligroin, petroleum ether), aromatic hydrocarbons (e.g. benzene, toluene, xylene), halogenated hydrocarbons
(e.g. chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, dichlorobenzene) , ethers (e.g. diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, diethylene glycol dimethyl ether), ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone), esters (e.g. ethyl formate, ethyl acetate, butyl acetate), nitro compounds (e.g. nitroethane, nitrobenzene), nitriles (e.g. acetonitrile, isobutyronitrile), tertiary amines (e.g. pyridine, triethylamine, N,N-diethylaniline, tributylamine, N- methylmorpholine) , acid amides (e.g. N,N-dirnethyl- formamide), sulfur compounds (e.g. dimethyl sulfoxide, sulfolane) and mixtures thereof. Generally, the reaction temperature ranges from 0°C to the boiling point of the solvent in any of the reactions (i) and (ii). The reaction time ranges from 1 to 24 hours for each reaction, and from about 1 to about 48 hours for the reactions (i) through (ii). After completion of the reaction, the reaction solution is after-treated as usual. That is, water is added to the solution which is then extracted with an organic solvent and concentrated, and if necessary, the product obtained is subjected to chromatography, distillation, recrystallization, etc. Thus, the desired present compound can be obtained.
The present compounds (I) include their stereoisomers having a herbicidal activity. The compound represented by the formula (II) can be produced by reacting a compound represented by the formula (VII) ,
wherein γi, Y2, Y3 and Z are as defined above, with an acid-halogenating agent or an active esterifying agent (hereinafter reaction (iii)), and reacting the resulting reaction product with the compound represented by the formula (V) (hereinafter reaction (iv)).
The above reactions (iii) and (iv) can be carried out according to the foregoing reactions (i) and (ii), respectively. The compound (VII) can be produced according to
Organic Syntheses, Collective Volume 5, P. 635 (1973) J. Am. Chem. Soc, 6£, 2341 (1947)
Sci. Pap. Inst. Phys. Chem. Res. Jpn., jjj5, 101 (1962) (CA 58-4515f (1963))
YAKUGAKU ZASSHI (Journal of Japan Pharmaceutical Science Association), £2, 1368 (1961) (CA 59-3892 (1963))
DE 2619641 (Hoechst AG, 1977)
J. Org. Chem., 3_8, 3431 (1973)
Justus Liebigs Ann. Chem., 388, 9 (1912) Bull. Acad. Pol. Sci. Ser. Sci. Chim. <A> 1935, 201, 205
Bull. Inst. Chem. Res., Kyoto Univ., &3 (2), 72-81 J. Org. Chem., 36 (13), 1843 (1971) The compound represented by the formula (IV) can be produced by reacting the compound (VII) with the compound (III) according to the foregoing reaction (A).
The present compounds (I) have an excellent herbicidal activity and some of them have excellent selectivity between crops and weeds.
That is, the present compounds, when used for foliar treatment and soil treatment in upland fields, ridge or no-cultivating area, exhibit a herbicidal activity against various weeds, such as, Polygonaceae wild buckwheat (Polyqonum convolvulus) , pale smartweed (Polyqonum lapathifolium) , Pennsylvania smartweed (Polyqonum pensylvanicum) , ladysthumb (Polyqonum persicaria) , curly dock (Rumex crispus) , broadleaf dock (Rumex obtusifolius) Portulacaceae common purslane (Portulaca oleracea) Caryophyllaceae common chickweed (Stellaria media) Chenopodiaceae common lambsquarters (Chenopodium album) , kochia (Kochia scoparia) Amaranthaceae redroot pigweed (Amaranthus retroflexus) , smooth pigweed (Amaranthus hybridus) Cruciferae wild radish (Raphanus raphanistrum) , wild mustard (Brassica kaber) , shepherdspurse (Capsella bursapastoris) Leguminosae hemp sesbania (Sesbania exaltata) , sicklepod (Cassia obtusifolia) , Florida beggarweed (Desmodium tortuosum) , white clover (Trifolium repens) Malvaceae velvetleaf (Abutilon theophrasti) , prickly sida (Sida spinosa) Violaceae field pansy (Viola arvensis) , wild pansy (Viola tricolor) Rubiaceae catchweed bedstraw (Galium aparine) Convolvulaceae ivyleaf morningglory (Ipomoea hederacea) , tall morningglory (Ipomoea purpurea) , entireleaf morningglory (Ipomoea hederacea var. inteqriuscula) , pitted morningglory (Ipomoea lacunosa) , field bingweed (Convolvulus arvensis) Labiatae red deadnettle (Lamiu purpureum) , henbit (Lamium amplexicaule) Solanaceae jimsonweed (Datula stramonium) , black nightshade (Solanum niqram) Scrophulariaceae birdseye speedwell (Veronica persica) , ivyleaf speedwell (Veronica hederaefolia) Compositae common cocklebur (Xanthium pensylvanicu ) , common sunflower (Helianthus annuus) , scentless chamomile (Matricaria inodora) , corn marigold
(Chrysanthemum seqetum) , pineappleweed (Matricaria matricarioides) , common ragweed (Ambrosia artemisiifolia) , giant ragweed (Ambrosia trifida) , horseweed (Eriqeron canadensis) Boraginaceae field forget-me-not (Myosotis arvensis) Asclepiadaceae common milkweed (Asclepias syriaca) Euphorbiaceae sun spurge (Euphorbia helioscopia) , spotted spurge (Euphorbia maculata) Gramineae barnyardgrass (Echinochloa crus-qalli) , green foxtail (Setaria viridis) , giant foxtail (Setaria faberi) , large crabgrass (Digitaria sanquinalis) , goosegrass (Eleusine indica) , annual bluegrass (Poa annua) , blackgrass (Alopecurus myosuroides) , wild oat (Avena fatua) , johnsongrass (Sorghum halepense) , quackgrass (Aqropyron repens) , downy brome (Bromus tectorum) , bermudagrass (Cynodon dactylon) , fall panicum (Panicum dichotomiflorum) , Texas panicum (Panicum texanum) , shattercane (Sorghum vulqare) Commelinaceae common dayflower (Commelina communis) Equisetaceae field horsetail (Equisetum arvense) , and Cyperaceae rice flatsedge (Cyperus iria) , purple nutsedge
(Cyperus rotundus) , yellow nutsedge (Cyperus esculentus) .
In addition, some of the present compounds give such no phytotoxicity as becoming a problem to main crops such as corn (Zea mays) , wheat (Triticum aestivum) , barley (Hordeum vulqare) , rice (Oryza sativa) , soybean (Glycine max) , cotton (Gossypium spp) , sugar beet (Beta vulqaris) , peanut (Arachis hypoqaea) , sunflower (Helianthus annuus) , rape (Brassica napus) , etc. and horticultural crops such as flower, ornamental plants and vegetables.
The present compound (I) also can safely be used for no-till cultivation in soybean fields, peanut fields, corn fields, etc., and some of them give such no phytotoxicity as becoming a problem to crops.
In flooding treatment in paddy fields, the present compounds exhibit a herbicidal activity against weeds such as Gramineae
Echinochloa oryzicola Scrophulariaceae common falsepimpernel (Lindernia procumbens) Lythraceae
Rotala indica, Ammannia multiflora Elatinaceae
Elatine triandra Cyperaceae smallflower umbrellaplant (Cyperus difformis) ,
Scirpus juncoides, needle spikerush (Eleocharis acicularis) , Cyperus serotinus, Eleocharis kuroquwai Pontederiaceae
Monochoria vaqinalis Alismataceae
Saqittaria py maea, Saqittaria trifolia, Alisma canaliculatum Potamogetonaceae roundleaf pondweed (Potamoqeton distinctus) , and Umbelliferae
Oenanthe javanica
Some of the present compounds give such no phytotoxicity as becoming a problem to a transplanted rice plant or a direct seeded rice plant in paddy field. The present compound (I) can be used as an active ingredient for herbicides used in orchards, pastures, turfs, forests, afforestation area and non- agricultural fields (e.g. water way, canal), etc.
When the present compound (I) is used as an active ingredient for herbicides, it is usually formulated before use into emulsifiable concentrates, wettable powders, suspension formulations, granules, water-dispersible granules, etc. by mixing with solid carriers, liquid carriers, surface active agents or other auxiliaries for formulation.
The content of the compound (I) as an active ingredient in these preparations is normally within a range of about 0.003 to 90% by weight, preferably of about 0.01 to 80% by weight.
Examples of the solid carriers are fine powders or granules of kaolin clay, attapulgite clay, bentonite, terra alba, pyrophyllite, talc, diatomaceous earth, calcite, walnut shell powders, urea, ammonium sulfate, synthetic hydrated silicon dioxide, etc.
Examples of the liquid carriers are aromatic hydrocarbons (e.g. xylene, alkylbenzene, methyl- naphthalene, phenylquinolylethane) , alcohols (e.g. isopropanol, ethylene glycol), esters (e.g. dialkyl phthalate), ketones (e.g. acetone, cyclohexanone, isophorone), mineral oils (e.g. machine oil), vegetable oils (e.g. soybean oil, cotton seed oil), dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, N- methylpyrrolidone, water, etc.
Examples of the surface active agents used for emulsification, dispersion, spreading, etc. are anionic surface active agents such as salts of alkyl sulfates, alkylsulfonates, alkylarylsulfonates, dialkyl sulfosuccinates, salts of polyoxyethylene alkylaryl ether phosphoric acid esters, etc., and nonionic surface active agents such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, etc. Examples of other auxiliary agents for formulation are lignosulfonates, alginates, polyvinyl alcohol, gum arabic, CMC (carboxymethyl cellulose), PAP (isopropyl acid phosphate), etc.
The present compound (I) is usually formulated and used in soil treatment, foliar treatment or flooding treatment before or after emergence of weeds. The soil treatment includes soil surface treatment, soil incorpo¬ ration treatment, etc. The foliar treatment includes, in addition to treatment of plants from above, directed treatment in which treatment is limited to weeds only so as not to adhere to crops.
Build-up of the herbicidal activity of the present compound (I) can be expected by using them in mixture with other herbicides. Further, the present compound (I) can also be used in mixture with insecticides, acaricides, nematocides, fungicides, bacteriocides, plant growth regulators, fertilizers, soil improvers, etc. When the present compound (I) is used as an active ingredient for herbicides, their dosage rate varies with weather conditions, preparation forms, when, how and where the treatment is carried out, weeds species to be controlled, crops species to be protected, etc. Usually, however, the dosage rate is from 1 gram to 10000 grams of the active ingredient per hectare, preferably from 3 grams to 5000 grams of the active ingredient per hectare. The herbicidal composition of the present invention formulated into the form of an emulsifiable concentrate, a wettable powder, a suspension formulation or water dispersible granules may ordinarily be employed by diluting it with water at a volume of about 10 to 1000 liters per hectare (if necessary, adjuvants such as a spreading agent are added to the water). The granules and some suspension formulations are usually applied without being diluted.
The adjuvants include, in addition to the foregoing surface active agents, substances such as polyoxyethylene resin acids (esters), lignosulfonates, abietates, dinaphthylmethanedisulfonates and vegetable oils (e.g. crop oil concentrate, soybean oil, corn oil, cotton seed oil, sunflower oil). The present invention will be illustrated in more detail with reference to the following production examples, formulation examples and test examples, which are not however to be interpreted as limiting the invention thereto.
First, production examples for the present compound (I) are shown.
Production Example 1
0.42 Gram of a 60% sodium hydride in oil was suspended in 15 ml of N,N-dimethylformamide and was cooled to 0-5°C. Then, a solution of 2.33 g of 2- hydroxy-l-(N,N-dimethylaminooxycarbonyl)naphthalene in 5 ml of N,N-dimethylformamide was dropped to the suspension.
After stirring at 0-5°C for 30 min., a solution of 1.92 g of 2-chloro-4,6-dimethoxy-l,3,5- triazine in 5 ml of N,N-dimethylformamide was added. The reaction solution was heated to room temperature and kept at the same temperature for 3 hours with stirring.
The reaction solution was poured into water and extracted with ethyl acetate. The organic layer was washed with saturated sodium chloride solution and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure and the residue obtained was subjected to thin-layer chromatography (silica gel, hexane/ethyl acetate 2:l(v/v)) to obtain 2.10 g of 2- { (4,6-dimethoxy-l,3,5-triazine-2-yl)oxy}-l-(N,N- dimethylaminooxycarbonyl)naphthalene (the present compound (2) ) . 1H-NMR ( CDCI3 ) δ : 2 . 77 ( s , 6H )
3 . 90 ( s , 6H ) 7 . 13-8. 05 (m, 6H )
Production Example 2 1.30 Grams of 2-{ (4,6-dimethoxypyrimidine-2- yl)oxy}-l-naphthoic acid was dissolved in 15 ml of N,N- dimethylformamide and 1.82 g of 2,4,6-triisopropyl- benzenesulfonyl chloride and 0.98 g of 1-methylimidazole were added thereto and stirred for 20 min. at room temperature.
N,N-dimethylformamide solution (0.47 g of N,N- dimethylhydroxylamine hydrochloride and 0.58 g of triethylamine dissolved in 5 ml of N,N-dimethyl- formamide) was added thereto and stirred for 1 hour at room temperature.
The reaction solution was poured into water and extracted with ethyl acetate. The organic layer was washed five times saturated sodium chloride solution and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure and the residue obtained was subjected to thin-layer chromatography (silica gel, hexane/ethyl acetate 2:1 (v/v)) to obtain 1.20 g of 2-{ (4,6-dimethoxypyrimidine-2-yl)oxy}-l-(N,N- dimethylaminooxycarbonyl)naphthalene (the present compound (1) ) .
1H-NMR (CDCI3) δ: 2.76 (s, 6H)
3.75 (s, 6H) 5 . 74 ( s , 1H )
7 . 24-8 . 15 (m, 6H)
Production Example 3
In the Production Example 1, 7-hydroxy-8-(N,N- dimethylaminooxycarbonyl)quinoline can be used instead of 2-hydroxy-l-(N,N-dimethylaminooxycarbonyl)naphthalene to obtain 7-{(4,6-dimethoxy-l,3,5-triazine-2-yl)oxy}-8- (N,N-dimethylaminooxycarbony1)quinoline.
Table 1 illustrates examples of the compound (I) which can be produced by the above procedure of Production Examples.
- Cont'd -
Cont'd
- Cont'd -
- Cont'd
Cont' Ήd -
- Cont' Ήd -
- Cont'd
- Cont'd -
- Cont'd -
- Cont'd -
Production Examples for the compound (II) and a starting material are shown below.
Production Example 4
3.76 Grams of 2-hydroxy-l-naphthoic acid was dissolved in 40 ml of tetrahydrofuran and 3.89 g of N,N'-carbonyldiimidazole was added to this solution. After stirring for 30 minutes at room temperature, 2.34 g of N-methyl-N-methylhydroxylamine hydrochloride and 2.91 g of triethylamine were added thereto. The resulting solution was stirred for 3 hours at room temperature, the reaction solution was poured into water, and extracted with ethyl acetate. The organic layer was washed with saturated sodium chloride solution and dried over anhydrous magnesium sulfate. The solvent was removed under reduced pressure to obtain 2-hydroxy- 1-(N,N-dimethylaminooxycarbonyl)naphthalene. 1H-NMR (CDCI3) δ: 3.02 (s, 6H)
7.00-7.88 (m, 6H) 10.95 (bs, 1H) Table 2 illustrates specific examples of the compound (II), which can be produced by using the corresponding starting materials.
- Cont'd - Table 2 (Cont'd)
- Cont'd - Table 2 (Cont'd)
Cont'd - Table 2 (Cont'd)
- Cont'd - Table 2 (Cont'd)
Formulation examples are shown below. In the examples, the present compound (I) is shown by Compound No. in Table 1, and parts are by weight.
Formulation Example 1 Fifty parts of any one of the present compounds
(1) - (122), 3 parts of calcium lignosulfonate, 2 parts of sodium lauryl sulfate and 45 parts of synthetic hydrated silicon dioxide are well mixed while being powdered to obtain a wettable powder.
Formulation Example 2
Ten parts of any one of the present compounds (1) - (122), 14 parts of polyoxyethylene styrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate, 35 parts of xylene and 35 parts of cyclohexanone are well mixed to obtain an emulsifiable concentrate.
Formulation Example 3
Two parts of any one of the present compounds (1) - (122), 1 part of synthetic hydrated silicon dioxide, 2 parts of calcium lignosulfonate, 30 parts of bentonite and 65 parts of kaolin clay are well pulverized and mixed. The resulting mixture is well kneaded with water, granulated and dried to obtain a granule.
Formulation Example 4
Twenty five parts of any one of the present compounds (2) and (15), 50 parts of polyvinyl alcohol (10% aq.) and 25 parts of water are mixed and wet-pulverized until the particle size decreases to 5 microns or less. Thus, a suspension formulation is obtained.
Formulation Example 5
Forty parts of the polyvinyl alcohol (10% aq.) and 5 parts of any one of the present compounds (1), (3), (81) and (82) go into emulsified-dispersion until the particle size decreases to 10 microns or less and then 55 parts of water is added to obtain emulsion in water.
It is shown by test examples that the present compounds are useful as an active ingredient for herbicides. In the examples, the present compound (I) is shown by compound No. in Table 1 and compounds used for comparison are shown by Compound symbol in Table 3.
Table 3
The herbicidal activity and phytotoxicity were evaluated in eleven stages, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10 by comparing germination and growth of test plants with those untreated. [0]: the states of germination and growth of test plants showed no difference. [10]: test plants either completely died or germination/growth were totally inhibited.
Test Example 1 Foliar treatment test in upland field Cylindrical plastic pots of 10 cm in diameter and 10 cm in depth were filled with upland field soil, and the seeds of plants in Table 4 were sowed in the pots and cultivated for 10 days in a greenhouse.
Thereafter, the test compounds were formulated into emulsifiable concentrates according to Formulation Example 2 and the prescribed amount of each emulsifiable concentrate was diluted with a spreading agent-containing water at a spray volume of 1000 liters/hectare and uniformly applied from above onto the whole foliar portion of the test plants by means of a sprayer. After application, the test plants were cultivated for 19 days in a greenhouse, and the herbicidal activity was examined. The results are shown in Table 4. Table 4
Test Example 2 Soil surface treatment test in upland field Cylindrical plastic pots of 10 cm in diameter and 10 cm in depth were filled with upland field soil, and seeds of plants in Table 5 were sowed in the respective pots and covered with soil. The test compounds were formulated into emulsifiable concentrates according to Formulation Example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water at a spray volume of 1000 liters/hectare and uniformly applied onto the whole soil surface by means of a sprayer. After application, the test plants were cultivated for 19 days in a greenhouse, and the herbicidal activity was examined. The results are shown in Table 5. Table 5
Test Example 3 Soil treatment test in upland field
Vats of 33 x 23 cm2 in area and 11 cm in depth were filled with upland field soil, and the seeds of the test plant shown in Table 6 were sowed in the respective vats and covered with soil in a thickness of 1 to 2 cm. The test compounds were formulated into emulsifiable concentrates according to Formulation Example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water at a spray volume of 1000 liters/ hectare and uniformly applied onto the whole soil surface by means of a sprayer. After application, the test plants were cultivated for 18 days in a greenhouse, and the herbicidal activity and phytotoxicity were examined. The results are shown in Table 6. Table 6
Test Example 4 Foliar treatment test in upland field
Vats of 33 x 23 cm2 in area and 11 cm in depth were filled with upland field soil, and seeds of test plants shown in Table 7 were sowed in the respective vats and cultivated for 30 days. Thereafter, the test compounds were formulated into emulsifiable concentrates according to Formulation Example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water at a spray volume of 1000 liters/hectare and uniformly applied from above onto the whole foliar portion of the test plants by means of a sprayer. The conditions of growth of the weed and crops at that time varied depending upon the kind of the test plants, but the test plants were in the 1- to 4-leaf stage and were 2 to 12 cm in height. Eighteen days after application, the herbicidal activity and phytotoxicity were examined. The results are shown in Table 7. This test was carried out in a greenhouse through the whole test period.
Table 7
Test Example 5 Foliar treatment test in upland field
Vats of 33 x 23 cm2 in area and 11 cm in depth were filled with upland field soil, and seeds of test plants shown in Table 8 were sowed in the respective vats and cultivated for 16 days. Thereafter, the test compounds were formulated into emulsifiable concentrates according to Formulation Example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water at a spray volume of 1000 liters/hectare and uniformly applied from above onto the whole foliar portion of the test plants by means of a sprayer. The conditions of growth of the weed and crops at that time varied depending upon the kind of the test plants, but the test plants were in the 1- to 4-leaf stage and were 2 to 15 cm in height. Eighteen days after application, the herbicidal activity and phytotoxicity were examined. The results are shown in Table 8. This test was carried out in a greenhouse through the whole test period.
Table 8
Test Example 6 Flooding treatment test in paddy field Wager's pots of 1/5000 ares were filled with paddy field soil, and seeds of test plants shown in Table 9 were sowed and covered with soil in a thickness of 1 to 2 cm. After creating a state of paddy field by water flooding, rice (at the 3-leaf stage) was transplanted and they were cultivated in a greenhouse. After 5 days (at the germination stage of barnyardgrass) , the test compounds were formulated into emulsifiable concentrates according to Formulation Example 2 and the prescribed amount of each of the emulsifiable concentrates was diluted with water and applied onto the water surface in the pots. Water leakage decreasing the depth of flooding water by 3 cm was carried out on the day subsequent to and two days after the application of test compounds. The test plants were cultivated for 20 days i'n a greenhouse. Then, the herbicidal activity and phytotoxicity were examined. The results are shown in Table 9.
Table 9
Test Example 7 Foliar treatment test in upland field
Vats of 33 x 23 cm2 in area and 11 cm in depth were filled with upland field soil, and seeds of test plants shown in Table 10 were sowed in the respective vats and cultivated for 30 days. Thereafter, the test compounds were formulated into emulsifiable concentrates according to Formulation Example 2, and the prescribed amount of each emulsifiable concentrate was diluted with water at a spray volume of 1000 liters/hectare and uniformly applied from above onto the whole foliar portion of the test plants by means of a sprayer. The conditions of growth of the weed and crops at that time varied depending upon the kind of the test plants, but the test plants were in the 1- to 4-leaf stage and were 2 to 12 cm in height. Eighteen days after application, the herbicidal activity and phytotoxicity wer-e examined. The results are shown in Table 10. This test was carried out in a greenhouse through the whole test period.
Table 10

Claims

CLAIMS :
1. A naphthol derivative represented by the formula (I)
wherein each of R1 and R2, which may be the same or different, represents a hydrogen atom, a C1-C6 alkyl group, a C3-C6 cycloalkyl group, or a phenyl group optionally substituted with at least one member selected from the group consisting of C1-C6 alkyl groups, halogen atoms, C1-C6 alkoxy groups, halo-C1-C6 alkyl groups, nitro groups, cyano groups and C1-C6 alkoxycarbonyl groups or a benzyl group optionally substituted with at least one member selected from the group consisting of C1-C6 alkyl groups, halogen atoms, C1-C6 alkoxy groups, halo-C1-C6 alkyl groups, nitro groups, cyano groups and C1-C6 alkoxycarbonyl groups, or R1 and R2 are bonded together at their ends to form a C4-C6 alkylene group, or R1 and R2 are bonded together at their ends to form a C4-C6 alkylene group containing an oxygen atom;
each of R3 and R4, which may be the same or different, represents a C1-C6 alkyl group, a C1-C6 alkoxy group or a halogen atom;
X represents CH or a nitrogen atom; Z represents CH or a nitrogen atom;
W represents an oxygen atom or a sulfur atom; each of Yi, Y2 and Y3, which may be the same or different, represents a hydrogen atom, a C1-C6 alkyl group, a halogen atom or a C1-C6 alkoxy group.
2. A naphthol derivative according to Claim 1, wherein each of R3 and R4, which may be the same of different, represents a C1-C6 alkoxy group.
3. A naphthol derivative according to Claim 1, wherein both R3 and R4 are methoxy groups.
4. A naphthol derivative according to Claim 1, wherein W represents an oxygen atom.
5. A naphthol derivative according to Claim 1, wherein each of R1 and R2, which may be the same or different, represents a hydrogen atom or a C1-C6 alkyl group; W represents an oxygen atom; each of Y1, Y2 and Y3, which may be the same or different, represents a hydrogen atom, a C1-C6 alkyl group or a halogen atom.
6. A naphthol derivative represented by the formula (II)
wherein R1, R2, Z, W, Y1, Y2 and Y3 are as defined in Claim 1.
7. A method for producing the naphthol derivative (I) according to Claim 1 which comprises reacting a naphthol derivative represented by the formula (II)
(wherein R1, R2, Y1, Y2, Y3, Z and W are each as defined in Claim 1) with a compound (III):
(wherein R3 and R4 are as defined in Claim 1 and W1 represents a halogen atom, a C1-C6 alkylsulfonyl group or a benzylsulfonyl group); or reacting [reaction (i)] the compound (IV)
(wherein R3, R4 , X, Y1, Y2, Y3, Z and W are as defined above) with an acid-halogenating agent or an active esterifying agent, and subsequently reacting [reaction (ii)] the resulting reaction product with a compound represented by the formula (V),
(wherein R1 and R2 are as defined above).
8. A herbicidal composition which comprises as an active ingredient, a herbicidally effective amount of the naphthol derivative (I) according to Claim 1 and an inert carrier or a diluent.
9. A method for controlling undesired weeds, which comprises applying a herbicidally effective amount of the naphthol derivative (I) according to Claim 1 to the area where undesired weeds grow or will grow.
10. A use of the naphthol derivative (I) according to Claim 1 as a herbicide.
EP93919629A 1992-09-29 1993-09-08 Naphthol derivatives, a method for producing the same and their use as herbicides Ceased EP0662963A1 (en)

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EP0223406B1 (en) * 1985-10-15 1990-08-29 Kumiai Chemical Industry Co., Ltd. Pyrimidine derivatives and herbicidal uses thereof
GB8808071D0 (en) * 1988-04-07 1988-05-11 Shell Int Research Triazine herbicides
ES2063075T3 (en) * 1988-06-16 1995-01-01 Basf Ag DERIVATIVES OF SALICILIC ACID AND ITS SULFURATED ANALOGS.
DE3832237A1 (en) * 1988-09-22 1990-03-29 Basf Ag AROMATIC CARBONATEURED DERIVATIVES, PROCESS FOR THEIR PREPARATION AND THEIR USE AS HERBICIDES
DE3919435A1 (en) * 1989-06-14 1990-12-20 Basf Ag SALICYLALDEHYDE AND SALICYLSAEED DERIVATIVES AND THEIR SULFUR ANALOGUE, PROCESS FOR THEIR MANUFACTURE AS HERBICIDES AND BIOREGULATORS
US5125957A (en) * 1989-11-01 1992-06-30 Sumitomo Chemical Company, Limited Pyrimidine derivatives
PH27460A (en) * 1989-12-28 1993-07-09 Kumiai Chemical Industry Co Pyrimidine derivatives and herbicidal composition containing the same
AU7324291A (en) * 1990-02-20 1991-09-18 Fmc Corporation 6-aryl-2-substituted benzoic acid herbicides
DE4034045A1 (en) * 1990-10-26 1992-04-30 Basf Ag salicylic acid derivatives

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