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 R ¹ and R2, which may be the same or different, represents a hydrogen atom, a C ₁ -C6 alkyl group, a C ₃ -C ₆ 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 C ₁ -C ₆ 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 C ₄ -Cβ alkylene group, or Ri and R2 are bonded together at their ends to form a C ₄ -C6 alkylene group containing an oxygen atom; each of R ³ 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 Y ¹ , Y ² and Y3 which may be the same or different, represents a hydrogen atom, a Cχ-C ₆ alkyl group, a halogen atom or a Ci-Cς, alkoxy group.

In the compound of the formula (I), each of R3 and R ⁴ , which may be the same or different, is preferably a Ci-Cε alkoxy, and more preferably both of R3 and R ⁴ 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~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-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, C ₁ -C ₆ 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-C _δ 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 C ₄ -C ₆ alkylene group include tetramethylene, pentamethylene and hexamethylene groups; and examples of the C ₄ -C ₆ alkylene group having an oxygen atom include -CH ₂ CH ₂ OCH ₂ CH ₂ -, -CH ₂ CH ₂ CH2OCH2CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ CH ₂ - 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. γ2 _f γ3, and Z are as defined above], with a compound represented by the formula (III),

[wherein X, R3 and R ⁴ 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, R ⁴ , 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, R ⁴ , 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; 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'-hydroxybenzisoxazolium tetrafluoroborate was used as said agent; and W ² 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, R ⁴ , 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, Y ² , 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 (CDCI ₃ ) 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 (CDCI ₃ ) 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 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

Test Example 4 Foliar treatment test in upland field

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.

Table 7

Test Example 5 Foliar treatment test in upland field

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.

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 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 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