DK144561B - HERBICIDE DIPHENYL ETHERE - Google Patents

Description

144561

The present invention relates to novel herbicidal diphenyl ethers.

Certain diphenyl ethers have been shown to be effective weed control agents. However, the herbicidal efficacy of a particular diphenyl ether cannot be predicted when assessing the substituent groups of the phenyl rings, and often quite closely related compounds will have quite different weed control capabilities. Various diphenyl ethers may have overlapping or complementary ranges of activity or selectivity and thus may be useful in combination for controlling different types of weeds by applying a mixture thereof. Furthermore, previously known diphenyl ethers are not quite effective as herbicides. An ideal herbicide will provide selective weed control throughout the growing season with a single dose at low dosage rates. The herbicide should be able to control all common types of weeds by killing them as seeds, as germinating seeds, as the seed, or as the plant growing. At the same time, the herbicide should not be phytotoxic to the crops on which it is applied and should be degraded or otherwise destroyed so that it does not permanently poison the soil.

As representative of the prior art, reference should be made to the description of U.S.A. No. 3,420,892, which discloses herbicidal activity for certain diphenyl ethers. Studies have shown that the compound 2-nitro-4-trifluoromethylphenyl-4-chlorophenyl ether known from this compound is unable to effectively control numerous single-seeded and two-seeded weed species at low dosage rates. The compounds of the invention are structurally related to the known compound, but are generally more effective and can combat numerous single-seeded and two-seeded weed species which cannot be contaminated with the known compound.

The herbicidal diphenyl ethers of the invention are peculiar in that they have the general formula CF, Λ o v Cl) φ,.

no 2 wherein X represents a halogen atom or a cyano group, Y represents a hydrogen atom or a halogen atom, and Z represents hydrogen, a hydroxy group, a C an alkoxy group, a C 1-4 alkyl group, a halogen atom, an amino group, a cyano group, a free acid or salt form carboxy group, a carbalkoxy group of up to 4 carbon atoms in the alkoxy moiety, an alkanoyloxy group of up to 4 carbon atoms, an alkyl substituted carboxy group up to 6 carbon atoms in the alkyl moiety, a C 1-4 alkoxy group substituted by halogen, alkenyl of up to 4 carbon atoms, alkynyl of up to 4 carbon atoms, hydroxy, alkoxy of up to 4 carbon atoms, alkylamino or dialkylamino of each of up to 4 carbon atoms, carboxy of free acid or salt form, carbalkoxy with up to 4 carbon atoms in the alkoxy moiety, alkanoyl with up to 4 carbon atoms in the alkyl moiety, alkylthio with up to 4 carbon atoms, carbamoyl, alkylcarbamoyl or dialkylcarbamoyl with each up to 4 alkyl carbon atoms, epoxy or alkylsulfonyl with up to 4 carbon atoms, or an amino group substituted by 1 or 2 alkanoyl groups, each containing up to 4 carbon atoms, 1 or 2 haloalkanoyl groups each having up to 4 carbon atoms, 1 or 2 alkylcarbamoyl groups each having up to 4 carbon atoms in the alkyl moiety, 1 or 2 alkylthiocarbonyl groups of the formula -CO-SR, wherein R is alkyl having up to 4 carbon atoms, 1 or 2 alkyl groups having up to 6 carbon atoms, or 1 or 2 hydroxyalkyl groups having a total of up to 6 carbon atoms, or Z represents a morpholino group.

As part of the preparation and testing of the compounds of this invention, compounds of the general formula (I) were first obtained in which Z represents a C1-6 alkoxy group, an alkyl group, a halogen atom, an acid carboxy group, a carbalkoxy group of up to 4 carbon atoms in the alkoxy moiety, an alkoxy alkoxy group having up to 4 carbon atoms in each alkoxy group, a hydroxy alkoxy group having up to 4 carbon atoms, a carboxyalkoxy group having up to 4 carbon atoms in the alkoxy moiety, a carbalkoxyalkoxy group having up to 4 carbon atoms in each alkoxy group, or an alkoxy group, or group having up to 4 carbon atoms in each alkyl group or with an alkanoyl group having up to 4 carbon atoms.

These compounds therefore represent preferred diphenyl ethers of the invention.

Due to particularly good herbicidal activity, according to the invention, compounds of formula (I) are preferred, wherein X represents Cl, Y hydrogen and Z hydrogen, an alkoxy group, a carboxy group in free acid or salt form, a carbalkoxy group having three carbon atoms in the alkoxy moiety or one having a carbalkoxy group having up to 4 carbon atoms substituted C 1-4 alkoxy group.

A particularly preferred compound of the invention is the compound of formula C1 wherein X represents chlorine, Y is hydrogen and Z is ethoxy. This compound exhibits particularly broad-spectrum, selective activity against grassy and two-seeded weed types when applied at rates of 0.25 to 1.0 kg / ha for crops such as soybean, cotton, peanut, sunflower, rice and wheat.

4 14Λ561

The above-mentioned diphenyl ethers are useful herbicides both before and after the emergence of the weeds. Herbicides for use before the emergence of the weeds are usually used to treat soil in which the desired utility plant must be planted by applying the herbicide either before sowing, during sowing or as in most applications after sowing / and before the crop emerges. Herbicides for treatment after the emergence of the weeds are the herbicides that are applied after the plants have emerged and during their growing season.

Among the useful plants to which the present diphenyl ethers can advantageously be used are e.g. cotton, soybeans, peanuts, color thistle, beans, peas, carrots, corn, wheat and other cereals.

The diphenyl ethers in question are useful for controlling weeds in rice fields. When used on planted rice plants, the ether can be applied either before or after the emergence of the weeds, i.e. they can be applied to the growing medium of the planted plants, either before the weeds emerge or while in their early stages of growth. Ethers. can be applied to the growth medium either before or after the rice has been planted in the medium.

The diphenyl ethers in question can be applied in any amount which gives the desired control of weeds. A preferred amount of application is from approx. 0.1 to approx. 13.4, preferably 0.3 to 4.5 kg diphenyl ether per acres.

Under certain conditions, the diphenyl ethers of the present invention may advantageously be incorporated into the soil or breathed growth medium before planting a utility plant. This incorporation can be carried out in any convenient manner, including by simple mixing with the soil, by applying the diphenyl ether to the soil surface and subsequently burying or milling it in the soil to the desired depth, or by using a liquid carrier medium to obtain of the necessary penetration and impregnation.

5 144561

The subject diphenyl ethers may be applied to the growth medium or plants to be treated either alone or as is usually done as a component of a herbicide or a formulation which also includes an agronomically useful carrier. Agronomically usable carrier is any substance which can be used for dissolving, dispersing or spreading the herbicidal compound in the mixture without impairing the effectiveness of the herbicidal compound and which itself has no adverse effect on the soil, equipment, crops or agronomic environment. The diphenyl ether compositions of this invention may also be used in any of these herbicidal formulations. The herbicidal mixtures of the present invention can be either solid or liquid formulations or solutions. Eg. For example, the diphenyl ethers may be formulated as wettable powders, emulsifiable concentrates, powders, granular formulations, aerosols or liquid emulsion concentrates. In such formulations, the compounds are stretched with a liquid or solid carrier; and, if desired, suitable surfactants are incorporated.

For the preparation of a herbicide preparation, a herbicide compound may be brought into a state suitable for this purpose, e.g. using a solid and / or liquid carrier, a surfactant, an adhesive or other pesticide, in which composition the herbicidal compound used is one or more of the aforementioned trihalo-methyl diphenyl ethers.

It is usually desirable, especially when applied after the emergence of the weeds; to include adjuvants such as wetting agents, spreading agents, dispersing agents, adhesives and adhesives in accordance with agro-culture practices. Examples of aids frequently used by those skilled in the art can be found in John W. McCutcheon, Inc. the publication "Detergents and Emulsifiers Annual".

The subject diphenyl ether compounds can be dissolved in any suitable solvent. Examples of solvents useful in the practice of the invention include alcohols, ketones, aromatic hydrocarbons, halogenated hydrocarbons, dimethylformamide, dioxane and dimethylsulfoxide. Mixtures of these solvents may also be used. The concentration of the solution may vary from approx. 2% to approx. 981, the preferred range being from ca. 25¾ to approx. 75¾.

6 144561

For the preparation of emulsifiable concentrates, the diphenyl ether can be dissolved in organic solvents such as benzene, toluene, xylene, methylated naphthalene, corn oil, pine oil, o-dichlorobenzene, isophorone, cyclohexanone or methyl oleate, or in mixtures of these solvents together with an emulsifier. which allows dispersion in water. Suitable emulsifiers include, e.g. The ethylene oxides are the derivatives of alkylphenols or long chain alcohols, mercaptans, carboxylic acids as well as reactive amines and partially esterified polyhydroxy alcohols. Sulfates and sulfonates soluble in solvents such as the alkaline earth salts or amine salts of alkyl benzene sulfonic acids and the sodium alcohols of the fatty alcohols with surfactant properties can be used as emulsifiers either alone or in combination with an ethylene oxide reaction product.

Liquid emulsion concentrates are similarly formulated into emulsifiable concentrates and include, in addition to the above components, water and a stabilizing agent such as a water-soluble cellulose derivative or a water-soluble salt of a polyacrylic acid. The concentration of the active component in emulsifiable concentrates is usually approx. 101 to approx. 601, and in liquid emulsion concentrates, this concentration may be as high as ca. 75¾.

Wettable powders suitable for atomization can be prepared by mixing the compound with a finely powdered solid such as clays, inorganic silicates and carbonates as well as silica species and incorporating wetting agents, weaving adhesives and / or dispersants into such mixtures. The concentration of the active components in such formulations is usually in the range of about

.201 to approx. 981, preferably ca. 401 to about 751. A dispersant may comprise ca. 0.5¾ to approx. 3¾ of the mixture, and a wetting agent may comprise from ca. 0.1¾ to approx. 5¾ of the mixture.

Powders may be prepared by mixing the compounds of the present invention with fine powdered / inert solids which may be of organic or inorganic nature. Useful materials for this purpose include e.g. vegetable dust, silica, silicates, carbonates and clays. A convenient method of making a powder is to dilute a wettable powder with a finely divided carrier. Powder concentrates are usually prepared containing about 2Q! to about 80®o active component, and these are then diluted to approx. in% to approx. 10¾ to the concentration of use.

Granulated formulations may also be prepared by impregnating a solid such as granulated diatomaceous earth, vermiculite, ground corn cobs, chaff, including bran or other chaff. A solution of one or more of the subject diphenyl ethers in a volatile organic solvent may be sprayed on or mixed with the granulated solid and the solvent may then be removed by evaporation. The granulated material may have any suitable grain size, the preferred grain range being from 16 to 60 mesh (US standard). The diphenyl ether will usually amount to approx. 2 to approx. 15¾ of the granulated formulation.

The diphenyl ethers in question may also be mixed with fertilizers or fertilizers prior to their dispersion. In a species of solid fertilizer mixture in which the diphenyl ethers may be used, the particles of the fertilizer or fertilizer components, such as ammonium sulfate, ammonium nitrate or ammonium phosphate, may be coated with one or more of the aforementioned ethers. The solid diphenyl ethers and solid fertilizer may also be mixed in mixing or mixing equipment or they may be incorporated with fertilizers in granulated formulations. Any ratio suitable to the crops and weeds to be treated can be used between the diphenyl ether and the fertilizer. The diphenyl ether will generally comprise from ca. 5¾ to approx. 25¾ of the fertilizer mixture. These mixtures provide fertilizers which promote the rapid growth of the desired plants and at the same time control the growth of undesirable plants.

The present diphenyl ethers can be applied as herbicidal sprays by the methods normally used, such as with normal high volume hydraulic spraying, low volume spraying, compressed air supported spraying, air spraying and powders. For low volume applications, a solution of the compound is usually used. The dilution and rate of application will usually depend on factors such as the nature of the equipment used, the method of application, the area to be treated, and the nature and stage of the weeds.

For certain applications, it may be desirable to add one or more other herbicides together with the diphenyl ethers. Examples of other herbicides which can be incorporated to obtain additional benefits and efficiencies include carboxylic acids and derivatives thereof, carbamic acid derivatives; phenols, substituted ureas, substituted triazines, diphenyl ether derivatives not subject to the present invention, anilides, uracils, nitriles and 1,1'-dimethyl-4,41-bipyridylium salts · U4561

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When herbicide mixtures are used, the relative ratios used will depend on the crop to be treated and the selectivity desired for control of the weeds.

The disclosed diphenyl ethers or their precursors can be prepared by any method known per se for analogous compounds. i.e. by reacting an appropriately substituted phenol or its potassium or sodium salt with an appropriately substituted phenyl halide, such as a chlorine or fluorobenzene in the presence of an alkaline agent.

The invention is illustrated in the following by way of example. In Table I, the typical diphenyl ethers (wherein Z = H) are listed with their melting points and elemental analyzes. In Table I, concrete illustrations of the compounds of Examples 1-3 and 6-8 are described for illumination.

Table II lists several of the typical diphenyl ethers with their melting points and elemental analyzes. For purposes of illustration, the specific preparations of the compounds of Examples 3Z, 7Z, 10Z, 19Z, 21Z, 25Z, 26Z, 49Z, 51Z, 55Z and 56Z are described in Table II, the letter Z being added to designate compounds wherein Z represents a group or an atom different from hydrogen.

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Example 1 10 144561

Preparation of 2-cyano-q, q, q-trifluoro-p-tolyl-4-nitrophenyl ether

A solution of potassium hydroxide (3.2 g, 0.05 mol of 89.3¾ purity) and p-nitrophenol (7.0 g, 0.05 mol) in methanol (25 ml) are evaporated under reduced pressure. The residue is dissolved in sulfolane, 4-chloro-3-cyano-q, q, q-trifluorotoluene (10.3 g, 0.05 mole) is added and the resulting solution is heated to 150 ° C for 5 hours. After cooling, the solution is diluted with benzene (350 ml), washed with water (6 x 250 ml), dried and the solvent removed. The residue (12.5 g) is recrystallized with isopropanol to give 2-cyano-q, q, q-trifluoro-p-tolyl-4-nitrophenyl ether (7.6 g, 49¾}, m.p. 93-98 ° C.

Example 2

Preparation of 2-chloro-q, q, q-trifluoro-p-tolyl-4-nitrophenyl ether 1α-2-chloro-q, q, q-trifluoro-β-cresol

Gaseous chlorine is passed through a gas flow meter into a solution of α, α, α-trifluoro-β-cresol (4.05 g, 0.025 mol) in ethylene dichloride (200 ml) at 0 ° C. until the theoretical volume has been absorbed. The solvent is distilled off and the residue distilled to give 2-ehloro-α, α, α-trifluoro-β-cresol (3.5 g, 71¾), bp 80-82 ° C at 33 mm Hg.

lb) 2-Chloro-q, q, q-trifluoro-p-tolyl-4-nitrophenyl ether

Potassium hydroxide (1.08 g, 0.0166 mol, 86¾ purity) is dissolved in methanol (10 ml) and a solution of 2-chloro-q, q, q-trifluoro-β-cresol (3.27 g, 0 0166 mol) in methanol is added. The solvent is removed under pressure and sulfolane (100 ml) is added followed by p-fluoro-nitrobenzene (2.34 g, 0.0166 mol) and the mixture is heated to 130-150 ° C for 7 hours. After cooling, the solution is poured into water (200 ml) and extracted with benzene. The extract is dried, filtered through activated silica gel (10 g) and the solvent removed. The residue is taken up in isopropanol / hexane (1: 3), cooled to -20 ° C and decanted off to an oily precipitate, whereupon the solvents are evaporated.

11 144561

The residue (2.9 g) is distilled to give 2-chloro-q, α, α-trifluoro-p-tolyl-4-nitrophenyl ether (1.6 g, 31¾), bp 23-8S ° C at 0.3 mm , which product, when crystallized, has a melting range of 62-68 ° C. An impurity isolated by a synthesis according to this method has been identified as 4-carbomethoxy-2-chlorophenyl-4-nitrophenyl ether.

lla) 2-Chloro-o, q, q-tr if luoro-p- to ly 1 -phenyl ether

Potassium phenoxide prepared by evaporation of a solution of phenol (4.7 g, 0.05 mol) and potassium hydroxide (3.3 g, 0.05 mol, 86.2 86 purity) in methanol (20 ml) is dissolved in sulfolane (75 g ) and 3,4-dichloro-α, α, α-trifluorotoluene (10.8 g, 0.05 mol) is added. The mixture is heated overnight at 170 ° C, cooled, diluted with benzene (250 ml) and washed with water (3 x 600 ml). The organic phase is dried, filtered through activated silica gel (20 g) and the solvent removed. The residue (12.4 g) is distilled to give 2-chloro-q, q, α-trifluoro-p-tolyl-phenyl ether (9.9 g, 72¾), bp 85-90 ° C / 0.25 mm contaminated with ca. 5¾ 6-chloro-q, q, q-trifluoro-m-tolyl-phenyl ether.

Calculated for C CHgClF₂O: C, 57.27; H, 2.95; Cl. 13.00; F. 20.91

Found: C, 57.13; H. 3.09; Cl. 13.17; F. 20.86.

11b) 2-Chloro-q, q, q-trifluoro-p-tolyl-4-nitrophenyl ether

A mixture of fuming nitric acid (10 g, 0.16 mol) and concentrated sulfuric acid (10 g) is first added with vigorous stirring at 75 ° C to 2-chloro-α, q, q-trifluoro-p-tolyl-phenyl ether (27 , 3 g, 0.01 mol), keeping the addition rate such that the temperature does not rise above 85 ° C. After a 1/2 hour stirring at 80 ° C, more mixed acid (5 g + 5 g) is added and the mixture is stirred for a quarter, cooled, diluted with water and extracted with benzene (2 x 200 ml). The extract is washed with water and hydrogen carbonate solution, dried and the solvent removed. The residue (29.1 g) is recrystallized with isopropanol to give 2-chloro-q, q, q-trifluoro-p-tolyl-4-nitro-phenyl ether (12.7 g, 40¾), m.p. 67-70 ° C. Analytical and spectroscopic data confirm the identity of the products of Methods I and II.

Example 3 12 144561

Preparation of 2, a, a, α-tetrafluoro-p-tolyl-4-nitrophenyl ether a) 2-Amino-α, q-, α-trifluoro-p-tolylphenyl ether 2-Nitro-q, q, α-trifluoro-β -tolylphenyl ether (57.0 g, 0.209 mol) is dissolved in ethanol (200 ml) and shaken in a hydrogen atmosphere in a Parr apparatus in the presence of platinum oxide (100 mg) until saturation is complete. The catalyst is removed by filtration and the solvent is evaporated to give 2-amino-q, q, α-trifluoro-p-tolyl-phenyl ether (50.3 g, 99¾), which is used without further purification.

Calcd for c. 61.66; H, 3.98; F. 22.51; N. 5.53

Found: C. 61.76; H. 3.65; F. 22.35; N. 5.52.

b) 2, a, a, a-tetrafluoro-p-tolylphenyl ether 2-Amino-q, a, a-trifluoro-p-tolylphenyl ether (25.3 g, 0.1 mol) is added to concentrated hydrochloric acid (100 ml), and the mixture is cooled to -15 ° C. With stirring, a solution of sodium nitrite (7.5 g, 0.1 + mol) in water (5 ml) is added dropwise, and after a total of 2 hours at -15 ° C, the diazonium chloride solution is filtered and treated with a solution of sodium fluoroborate ( 25 g, 0.2 + mole) in water (30 ml) and the full fluoroborate salt is filtered off, washed with ethanol and ether and air dried to give a yield of 23.0 g, decomposition point / -190 ° C. The salt is then added gradually to a flask in an oil bath at 200 ° C and when the decomposition is complete, the residue is taken up in benzene (150 ml), washed with water (4 x 100 ml), dried and the solvent removed. The residue (10.3 g) is extracted with isopropanol / hexane to give a residue which after distillation provides 2, α, α, α-tetrafluoro-p-tolylphenyl ether (3.4 g, 14,) , 25 mm.

c) 2, α, α, α-tetrafluoro-β-toly1-4-nitrophenyl ether

The above substance is nitrated by the procedure described above in Example 2 for 2-chloro-α, α, α-tetrafluoro-p-tolyl-4-nitrophenyl ether.

Example 5 13 U4561

Preparation of 2,6-dichloro-α, α, α-trifluoro-p-tolyl-4-nitrophenyl ether a) 3,4-Dichloro-q, q, q-trifluoro-5-nitrotoluene and 5,4-dichloro-q , q, a-trifluoro-6-nitrotoluene

A mixture of 3,4-dichloro-α, α, α-trifluoro-toluene (430 g, 2.0 mole), concentrated sulfuric acid (1200 ml) and concentrated nitric acid (1200 ml, excess) was stirred for 1/2 hour at 90 DEG. 100 ° C. The mixture was then cooled and the acid phase was discarded. The organic phase is washed with water, dilute sodium bicarbonate solution, potassium carbonate solution, dried and distilled to form a mixture containing almost equal amounts of 3,4-dichloro-α, q, q-trifluoro-5-nitrotoluene and 3,4-dichloro -a, a, a-trifluoro-6-nitrotoluene (456 g, 89%), boiling point 86 ° C / 3 mm.

b) 2-Chloro-q, ct, q-trifluoro-6-nitro-p-tolylphenyl ether

A solution of potassium hydroxide (43.2 g of 861 purity, 0.665 mol) in water (20 ml) was slowly added to a solution of phenol (62, 5 g, 0.665 mol) and the product of (a) above (450 g total, equivalent to 0.665 moles of 3,4-dichloro-q, q, q-trifluoro-5-nitrotoluene) in sulfolane (300 ml) at 30-68 ° C with stirring. After stirring for a total of 1 hour at 42-68 ° C, the mixture was diluted with hexane (400 ml) and water (600 ml). The resulting layers were separated and the aqueous phase was extracted once with hexane. The combined organic phases were washed with water and dilute sodium hydroxide solution, dried, and the solvent removed. The residue (471.3 g) was distilled through a Vigreux column with vacuum jacket. Fraction # 1 (272.2 g) with boiling point less than 100 ° C / 0.2 mm consisted essentially of unreacted 3,4-dichloro-q, a, q-trifluoro-6-nitro-toluene. Fraction # 2 (196.2 g) of boiling point 109-119 ° C / 0.2 mm consisted essentially of the pure desired diphenyl ether. A small residue (3.5 g) was discarded. Fraction # 2 was crystallized and recrystallized with 2-propanol (600 ml) at 0 ° C to give 2-chloro-α, α, α-trifluoro-6-nitro-p-tolylphenyl ether (144 g, 68%), m.p. 5 7-61 ° C.

C) 2-Amino-6-chloro-α, α, α-trifluoro-β-tolylphenyl ether

A solution of 2-chloro-α, α, α-trifluoro-6-nitro-p-tolylphenyl ether (150 g, 0.472 mol) in ethanol (1200 ml) was shaken in a hydrogen atmosphere in a Parr apparatus in the presence of Pt C (600 mg) until the recording stopped. The catalyst was filtered off, the solvent was removed, and the residue was taken up in pentane (600 ml) and filtered through activated silica gel (/ v / 15 g) and the solvent was removed. The residue was recrystallized with pentane at -20 ° C to give 2-amino-6-chloro-q, q, q-trifluoro-p-tolylphenyl ether (94.1 g, 701), mp 47-53 ° C.

d) 2,6-Dichloro-q, q, q-trifluoro-p-tolylphenyl ether 2-Amino-6-chloro-α, α, α-trifluoro-p-tolylphenyl ether (5.8 g, 0.02 mol) with concentrated hydrochloric acid (70 ml) to form a suspension of the amine hydrochloride. At -15 ° C, the suspension was added dropwise with stirring a solution of sodium nitrite (1.5 g, 0.022 mol) in water (3 ml), then the mixture was stirred for 50 minutes at +3 - -10 ° C and then filtered through a sintered glass filter. The filtrate was slowly added to a suspension of cuprous chloride (3.0 g) in concentrated hydrochloric acid (20 ml) at -3 - -10 ° C and then the temperature was slowly raised to 90 ° C over 20 minutes. The mixture was then cooled and neutralized with solid sodium bicarbonate and extracted with ether. The extracts were washed with water and sodium carbonate solution, dried and evaporated. The residue was distilled to give the diphenyl ether (3.5 g) as an oil which crystallized. The solid was taken up in pentane (10 ml) and filtered through activated silica gel ('-'-' 5g) and the solvent removed. The residue (3.3 g) was recrystallized with 2-propanol to give 2,6-dichloro-α, α, α-trifluoro-p-tolylphenyl ether (2.75 g, 451), mp 48-50 ° C.

e) 2,6-Dichloro-q, q, q-trifluoro-p-tolyl-4-nitrophenyl ether 2,6-Dichloro-q, α, α-trifluoro-p-tolylphenyl ether (1.7 g, 0.0055 mol ) was added to a cold (0 ° C) mixture of concentrated sulfuric acid (1.7 g) and concentrated nitric acid (1.2 g). The mixture was heated to 30-35 ° C and stirred at that temperature for 30 minutes, then diluted with water and extracted with benzene / pentane and the extract washed with sodium hydrogencarbonate solution and water, then dried and evaporated. The residue was combined with the result of a similar experiment with 500 mg of starting material and recrystallized with 2-propanol to give 2,6-dichloro-α, α, α-trifluoro-p-tolyl-4-nitrophenyl ether (1.9 g, 75¾) , mp 83-86 ° C.

It should be noted that the diphenyl ethers in question can also be properly designated using other nomenclature systems. Eg. For example, the diphenyl ether of Example 1 can also be referred to as 2-cyano-4-trifluoro-methyl-4'-nitrodiphenyl ether.

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m 21 U4561

Example 1Z

Preparation of 2,6-dichloro-q, ct, α-trifluoro-p-tolyl-3-ethoxy-4-nitrophenyl ether a) 3,4-Dichloro-5-nitro-ethyl, α, α-trifluorotoluene 3.4 Dichloro-α, α, α-trifluorotoluene (862 g, 4.0 mol) is added with stirring to a mixture of concentrated sulfuric acid (4400 g) and nitric acid (3400 g) at 35 ° C. The mixture is stirred for 70 minutes at 95 ° C and allowed to separate. The oil layer is washed once with water and twice with 5¾ sodium carbonate solution, dried and fractionated to form 3,4-dichloro-5-nitro-α, α, a4rifluorotoluene (188 g, 18¾), boiling point 115-118 ° C / 15 mm , 88¾ pure.

b) 5-Amino-3,4-dichloro-α, α, α-trifluorotoluene 500 ml of an ethanolic solution containing 3,4-dichloro-5-nitro-α, α, α-trifluorotoluene (188 g, 0.72 mole) and platinum oxide (Adams catalyst) (0.2 g) are reduced at room temperature in a low pressure hydrogenation apparatus to give 5-amino-3,4-dichloro-α, α, α-trifluorotoluene (129.9 g, 78¾) . boiling point 65-70 ° C / l-2 mm.

c) 3,4,5-Trichloro-α, α, q-trifluorotoluene

A solution of sodium nitrite (39 g) in water (85 ml) is added over 1 hour to a solution of 5-amino-3,4-dichloro-ct, α, α-trifluorotoluene (117.5 g, 0 (51 mol) in 1700 ml of concentrated hydrochloric acid at -6 ° C and the solution is stirred for 1 hour, after which it is filtered. The filtrate is added to a solution of cuprous chloride (76.5 g) in concentrated hydrochloric acid (500 ml) over 5 minutes at 0-8 ° C and gradually heated to 80 ° C over 80 minutes. The reaction mixture is cooled to 35 ° C and extracted with hexane (2 x 300 ml). The extract is washed with water, 2¾ sodium hydroxide solution, dried and distilled to give 3,4,5-trichloro-α, α, α-trifluorotoluene (70 g, 55¾), bp 82-86 ° C / 10 mm, 95¾ pure.

D) 1,3-615 (2,6-dichloro-α, α, α-trifluoro-β-tolyloxy) benzene

A mixture of 3,4,5-trichloro-α, α, α-trifluoro-toluene (10 g, 0.04 mole) and the dipotassium salt of 1,3-dihydroxybenzene (4 g, 0.021 mole) in 150 ml of sulfolane is stirred and heated for 70 minutes to 120 ° C. The cooled reaction mixture is diluted with benzene (350 ml) and washed once with water (100 ml). Hexane (200 mL) is added and the solution washed with water (3 x 500 mL), filtered through activated silica gel (/ - 25 g) and the solvents removed. The oil residue is crystallized from a mixture of pentane and benzene to give 1,3-bis (2,6-dichloro-α, α, α-trifluoro-β-tolyloxy) benzene (5.3 g, 49¾), m.p. 121-122 ° C.

e) 1,3-Bis (2,6-dichloro-α, α, α-trifluoro-β-tolyloxy) -4-nitrobenzene

A cooled mixture of concentrated sulfuric acid (6.5 mL) and nitric acid (4.4 mL) was added with stirring to an ice-cold solution of 1,3-bis (2,6-dichloro-α, α, α-trifluoro-β tolyloxy) benzene (11.1 g, 0.021 mol) in 1,2-dichloroethane (30 ml). After 30 minutes at room temperature, the phases are allowed to separate and the organic phase is washed 2 times with water. Benzene (200 ml) is added and the solution is washed twice with dilute sodium carbonate solution, dried, filtered through activated silica gel (a / 25 g). and the solvents are removed. The remaining crystals are triturated with pentane, filtered and dried to give 1,3-bis (2,6-dichloro-α, α, α-trifluoro-β-tolyloxy) -4-nitrobenzene (9.9 g, 82¾), mp 137.5-140.5 ° C, 90¾ pure.

f) 2,6-Dichloro-α, α, α-trifluoro-p-tolyl-3-ethoxy-4-nitrophenyl ether

A solution of potassium hydroxide, 86¾ (1.9 g, 0.029 mol) in ethanol (20 ml) is added to a solution of 1,3-bis (2,6-dichloro-α, α, α-tri-fluoro-β tolyloxy) -4-nitrobenzene (8.0 g, 0.014 mol) in p-dioxane (70 ml) and heated for 1 hour to 50 ° C. The solution is cooled and benzene (^ 250 ml) is added and the crystals of potassium 2-nitro-5- (2,6-dichloro-α, α, α-trifluoro-p-tolyloxy) phenoxide (2.9 g, 52¾) is collected. Acid treatment provides the free phenol, 2,6-dichloro-α, α, α-trifluoro-β-tolyl-3-hydroxy-4-nitrophenyl ether (2.0 g, 40¾), m.p. 84.5-86.5 ° C. This phenol (1.7 g, 0.0046 mol) is converted to the potassium salt, dissolved in dimethylformamide (20 ml) and treated with ethyl iodide (1.2 g, 0.0077 mol) for 2 1/2 time to 50-70 ° C. The reaction mixture is diluted with benzene (1007 100 ml) and hexane (rv> 50 ml) washed with water (3 x 100 ml), dried, filtered through activated silica gel (^ 15 g) and the solvents removed to form 2,6-dichloro -a, a, oc-trifluoro-p-tolyl-3-ethoxy-4-nitrophenyl ether (0.8 g, 44¾)) mp 100.5-102 ° C.

Ethyl 2,6-dichloro-α, α, α-trifluoro-p-tolyl ether (3.0 g, 82¾) is recovered from the filtrate from the 2.9 g phenoxide. boiling point 78 ° C / 5 mm and an additional amount of the product 2,6-dichloro-α, α, α-trifluoro-p-tolyl-3-ethoxy-4-nitrophenyl ether (0.35 g, 6 $), m.p. 88 -93 ° C.

24

Example 3Z

U4561

Preparation of 2-chloro-α, α, α-trifluoro-p-tolyl-5-ethoxy-4-nitrophenyl ether

Process A

a) 1,3-Bis (2-chloro-q, q, q-trifluoro-p-tolyloxy) benzene

A solution of potassium hydroxide (3.26 g, 0.05 mol, 85¾) in water 0% / 3 g) is slowly added dropwise to a solution of resorcinol (2.75 g, 0.025 mol) and 3,4-dichloro-q , q, α-Trifluorotoluene (10.75 g, 0.05 mol) in sulfolane (125 ml) at 150-160 ° C with stirring. When the addition is complete, the vigorously colored reaction mixture is stirred overnight at 150-160 ° C, cooled, diluted with benzene (200 ml) and gently washed with water (700 ml). Hexane (200 ml) is added and the mixture is washed with water (600 ml), dilute sulfuric acid (600 ml), dilute sodium hydroxide solution (600 ml) and water (600 ml), then dried and the solvent removed to give 1, 3-bis (2-chloro-α, α, α-trifluoro-β-tolyloxy) benzene (8.6 g, 651), bp 160-170 ° C / 0.1 mm.

b) 1,3-Bis (2-chloro-α, α, q-trifluoro-β-tolyloxy) -4-nitrobenzene 1,3-Bis (2-chloro-q, q, q-trifluoro-β-tolyloxy) benzene (12 g, 0.0255 mol) is added to a mixture of concentrated nitric acid (12 g) and sulfuric acid (15 g) at 5 ° C. The temperature is then allowed to rise to 25-30 ° C with manual stirring and gentle cooling in an ice bath, and after 10-20 minutes the oil solidifies. The mixture is taken up in water / benzene (400 ml) / hexane (400 ml) and the organic phase is washed with water, dried, filtered through activated silica gel (^ 20 g) and the solvents removed. The residue is recrystallized from isopropanol to give 1,3-bis- (2-chloro-α, q, q-trifluoro-p-tolyloxy) -4-nitrobenzene (7.4 g, 56¾), mp 110-111.5 ° C.

c) 2-Chloro-q, q, q-trifluoro-p-tolyl-3-ethoxy-4-nitrophenyl ether

A 10¾ potassium hydroxide solution in ethanol (10 ml) is added to a solution of 1,3-bis (2-chloro-q, q, q-trifluoro-p-tolyloxy) -4-nitrobenzene (2 g, 0.0039 mol ) in dioxane (20 ml). After 40 minutes at room temperature, the solution is heated to 45 ° C for 8 minutes, then cooled, diluted with benzene (50 'ml) and hexane (50ml) and washed with water, dried, and the solvents removed. The residue is recrystallized with isopropanol to give 2-chloro-α, α, α-trifluoro-p-tolyl-3-ethoxy-4-nitrophenyl ether (1.21 g, 86¾), mp 83-84 ° C.

Method B

a) 2-Chloro-α, q, α-trifluoro-p-tolyl-3-hydroxyphenyl ether

A mixture of resorcinol's potassium salt (186.3 g, 1 mol), 3,4-dichloro-α, α, α-trifluorotoluene (53.7 g, 0.25 mol), and sulfolane (100 ml) is stirred 30 hours at 140-160 ° C.

Benzene (500 ml) and water (200 ml) are added and the organic phase is washed with water (3 x 200 ml), diluted with hexane (500 ml) and washed again with water, then dried, filtered through activated silica gel ( 15 g), the solvents are removed and the residue distilled to give 2-chloro-α, α, α-trifluoro-p-tolyl-3-hydroxyphenyl ether (45.1 g, 621), bp 112-124 ° C. o, 3 mm.

b) 2-Chloro-a, a, q-trifluoro-p-tolyl-3-acetoxyphenyl ether

A mixture of 2-chloro-α, α, α-trifluoro-p-tolyl-3-hydroxyphenyl ether (184 g) and acetic anhydride (334 g) is heated on a steam bath for 1 hour and cooled. The mixture is washed with 5¾ sodium carbonate solution (2 x 500 ml) and distilled to give 2-chloro-α, α, α-trifluoro-p-tolyl-3-acetoxyphenyl ether (84 g, 40¾), bp 107-117 ° C / o , 09 mm.

c) 2-Chloro-α, α, α-trifluoro-p-tolyl-3-acetoxy-4-nitrophenyl ether

A solution of 2-chloro-α, α, α-trifluoro-p-tolyl-3-acetoxyphenyl ether (249 g, 0.75 mol) in 1,2-dichloroethane (1200 ml) is stirred for 2.2 hours at 20-30 ° C with a cooled mixture of concentrated sulfuric acid (276 g) and nitric acid, 70¾ (227 g). Hexane (700 ml) is added and the oil layer is washed once with water, three times with dilute sodium bicarbonate and again with water, then dried, filtered through activated silica gel (^ 40 g) and the solvents removed. The product is recrystallized with hexane-benzene to give 2-chloro-α, α, α-trifluoro-p-tolyl-3-acetoxy-4-nitrophenyl ether (207.5 g, 73¾), mp 83-89 ° C.

D) 2-Chloro-α, α, α-trifluoro-p-tolyl-3-hydroxy-4-nitrophenyl ether

A solution of 2-chloro-α, ct, α-trifluoro-p-tolyl-3-acetoxy-4-nitro-phenyl ether (204.9 g, 0.545 mol) in methanol (2900 ml) is stirred for 1 hour at 20 ° C. ° C with potassium carbonate (103 g, 0.745 mol). Remove 90¾ of the methanol and add benzene (1 liter), 7-8¾ sulfuric acid solution (1600 ml) and stir for 1 1/2 hours at 25 ° C. The oil layer is washed twice more with water (200 ml per time), dried, filtered through activated silica gel (40 g), the solvents removed and the residue crystallized from hexane to give 2-chloro-α, α, α-trifluoro-β -tolyl-3-hydroxy-4-nitrophenyl ether (165.3 g, 90 °), m.p. 68.5-73 ° C.

e) 2-Chloro-α, α, α-trifluoro-p-tolyl-3-ethoxy-4-nitrophenyl ether

A solution of 2-chloro-α, α, α-trifluoro-β-trifluoro-β-tolyl-3-hydroxy-4-nitrophenyl ether (60 g, 0.018 mol, 731 purity) and dimethylformamide (100 g) is converted to The potassium phenoxide and stirred with ethyl bromide (35 g, 0.32 mol) for 3 hours at 60 ° C and 5 hours at 80 ° C are added perchlorethylene (150 g) and the solution is washed twice with water 250 ml per ml. at 50 ° C. The solvents are removed to form 2-chloro-α, α, α-trifluoro-p-tolyl-3-ethoxy-4-nitrophenyl ether (56 g, 831, 71¾ purity).

Example 7Z

Preparation of 2-cyano-α, α, ot-trifluoro-p-tolyl-3-ethoxy-4-nitrophenyl ether

A solution of potassium hydroxide (2.6 g, 0.04 mole) of 87.3¾ purity and 3-ethoxy-4-nitrophenol (7.3 g, 0.04 mole) in methanol (30 ml) is evaporated to dryness while reducing pressure. A residue of potassium 3-ethoxy-4-nitrophenoxide is dissolved in sulfolane (200 g) and 4-chloro-3-cyano-benzotrifluoride (8.2 g, 0.04 mol) is added. Gas chromatography (G1C) shows that the reaction is complete after 4 1/2 hours of stirring at 110 ° C and 2 1/2 hours of stirring at 135 ° C. The reaction mixture is cooled and poured into deionized water and the precipitate which is formed is filtered off and air dried. Recrystallization with isopropanol provides 2-cyano-α, α, α-trifluoro-p-tolyl-3-ethoxy-4-nitrophenyl ether (7.4 g, 531), mp 143-145 ° C.

27 144561

Example 19Z

Preparation of 2-chloro-ot, ot, q-trifluoro-p-tolyl-3-ethyl-amino-4-nitrophenyl ether

A solution of 1,3-bis (2-chloro-α, α, α-trifluoro-β-tolyloxy-4-nitrobenzene (12.8 g, 0.025 mol) and ethylamine (6.7 g, 0.15 mol) in dioxane (120 ml) is heated in a pressure vessel to 50-55 ° C for 4 1/2 hours and 4.3 hours to 90-95 ° C. Benzene (200 ml), hexane (70 ml) and water ( 500 ml) and the organic phase is washed with water (500 ml), 10¾ sodium bicarbonate solution (200 ml) and water (200 ml), dried, filtered through activated silica gel (25 g), the solvents removed and the residue recrystallized from hexane to give 2-chloro-α, α, α-trifluoro-p-tolyl-3 “ethylamino-4-nitrophenyl ether (7.9 g, 88¾), mp 82-83 ° C.

Example 21Z

Preparation of 2-chloro-α, α, α-trifluoro-p-tolyl-3-diethylamino-4-nitrophenyl ether

A solution of 1,3-bis (2-chloro-α, α, α-trifluoro-β-tolyloxy) -4-nitrobenzene (12.8 g, 0.025 mol) in p-dioxane (130 ml) is heated at reflux 26 hours at 65-95 ° C with diethylamine (50 g, 0.55 mol). Add benzene (^ 200 ml) and water (^ 500 ml) followed by hexane (+/- 70 ml) and the oil layer is separated, washed with water (500 ml), 10¾ sodium bicarbonate solution (200 ml) and water (200 (ml), then dried, filtered through activated silica gel (~ -25 g) and the solvents removed. 0.1 e residue is distilled in vacuo to give 2-chlpr 2 C / 0.01 mm.

Example 25Z

Preparation of 2-chloro-ot, a, q-trifluoro-p-tolyl-3- (1-carboxyethoxy) -4-nitrophenyl ether 2-Chloro-α, q-trifluoro-p-tolyl-3- (1- carbethoxyethoxy) -4-nitrophenyl ether (8.6 g, 0.02 mol), potassium hydroxide, 86¾ (2.6 g, 0.04 mol), ethanol (8 ml), dioxane (8 ml) and water (100 ml) is heated to 90-95 ° C for 30 minutes. Ether (200 ml) and water (200 ml) are added and the mixture is acidified with dilute sulfuric acid, then the aqueous layer is extracted three times with ether (200 ml per time), the extracts are dried and the ether is removed to give 2 -chloro-α, α, α-trifluoro-p-tolyl-3- (1-carboxyethoxy) -4-nitrophenyl ether (6.4 g, 79%), m.p. 108-109 ° C.

Example 26Z

Preparation of 2-chloro-α, α, α-trifluoro-p-tolyl-3- (1-carbethoxyethoxy) -4-nitrophenyl ether

Potassium 2-nitro-5- (2-chloro-α, α, α-trifluoro-β-tolyloxy) phenoxide (7.4 g, 0.02 mol), ethyl 2-bromopropionate (3.6 g, O (02 mol) and sulfolane (50 ml) are heated for 1 1/2 hours at 90-95 ° C. Benzene (100 ml) and hexane (100 ml) are added and the solution is washed with dilute sodium carbonate solution, then with water, dried and the solvents removed. The residue is crystallized from pentane to give 2-chloro-α, α, α-trifluoro-p-tolyl-3- (1-carbethoxyethoxy) -4-nitrophenyl ether (6.2 g, 71¾), mp 71-74 ° C.

Example 49Z

Preparation of 2-chloro-α, α, α-trifluoro-p-tolyl-3-carbo-methoxy-4-nitrophenyl ether a) 3-Cyano-4-nitrofluorobenzene m-Fluorobenzonitrile (96.8 g, 0.8 mol) over 2 1/2 hours to a mixture of concentrated sulfuric acid (600 ml) and potassium nitrate (80.9 g, 0.8 mol) at 3-6 ° C, then allow the mixture to warm to 25 ° C. The mixture is poured onto crushed ice (3000 ml), extracted with chloroform (5 x 250 ml), dried and the solvent removed. The residue is extracted with pentane and dried to give 3-cyano-4-nitro-fluorobenzene (115 g, 86.5%), mp 102-104 ° C.

b) 2-Chloro-α, cc, α-trifluoro-p-tolyl-3-cyano-4-nitrophenyl ether____

The potassium phenoxide of 2-chloro-α, α, α-trifluoro-β-cresol (13.5 g, 0.0688 mol) prepared in sulfolane at 5 ° C is added to a solution 29 of 3-cyano-4-nitrofluorobenzene (11.4 g, 0.0688 mol) in sulfolane at 120 ° C over 4 hours, then stir for 18 hours and cool.

Benzene (200 ml) and hexane (100 ml) are added and the solution washed with water (5 x 250 ml), dried, filtered and the solvents removed. The residue is crystallized to give 2-chloro-α, α, α-β-tolyl-3-cyano-4-nitrophenyl ether (16.3 g, 69¾), mp 95-103 ° C, 85¾ purity.

c) 2-Chloro-a, a, a-trifluoro-p-tolyl-3-carboxy-4-nitrophenyl ether 2-chloro-a, a, a-trifluoro-p-tolyl-3-cyano-4-nitrophenyl ether (11.2 g, 0.0327 mol), acetic acid (25 ml) and hydrogen bromide (12 ml with 47.81 purity) are heated at 120 ° C in a pressure vessel for 2 days, after which the contents are poured over crushed ice and extracted with benzene (2 x 150 ml). The benzene solution is dried, filtered, the solvents removed and the residue crystallized from pentane to give 2-chloro-α, α, α-trifluoro-p-tolyl-3-carboxy-4-nitrophenyl ether (7.5 g, 63.51), mp 140-150 ° C, 85¾ purity.

d) 2-Chloro-α, α, α-trifluoro-p-tolyl-3-carbomethoxy-4-nitrophenyl ether

Hydrogen chloride is bubbled through a solution of 2-chloro-α, α, α-trifluoro-p-tolyl-3-carboxy-4-nitrophenyl ether (2.3 g, 0.0064 mol) in methanol (50 ml) in 10 hours at 32 ° C, then stir overnight and the solvents removed to form 2-chloro-α, α, α-trifluoro-p-tolyl-3-carbomethoxy-4-nitrophenyl ether (1.5 g, 50¾) .

Example 51Z

Preparation of 2-chloro-α, g, q-trifluoro-p-tolyl-3- (1-carbamoylethoxy) -4-nitrophenyl ether a) 2-Chloro-α, α, α-trifluoro-p-tolyl-3- ( 1-Chloro-methyl-ethoxy) -4-nitrophenyl ether 2-Chloro-α, α, α-trifluoro-p-tolyl-3- (1-carboxyethoxy) -4-nitrophenyl ether (34.8 g, 0.086 mole), thionyl chloride (20 (4 g, 0.172 mol) and benzene (150 ml) are stirred for 5 hours at 95 ° C and for 16 hours at 25 ° C. The benzene is removed to form 2-chloro-α, α, α-trifluoro-p-tolyl-3- (1-chloroformylmethoxy) -4-nitrophenyl ether (33.4 g, 92¾).

B) 2-Chloro-ct, a, a-trifluoro-p-tolyl-3- (1-carbamoylethoxy) -4-nitrophenyl ether

A solution of 2-chloro-α, α, α-trifluoro-p-tolyl-3- (1-chloroformyl-ethoxy) -4-nitrophenyl ether (4.2 g, 0.01 mol) in ether (50 ml) is added. to an ether solution (200 ml) saturated with ammonia gas at temperatures below 0 ° C. After 30 minutes, water (100 ml) is added and the ether layer is separated. The aqueous phase is extracted with ether (3 x 200 mL) and the combined extracts are dried, filtered through activated silica gel (^ 20 g) and the solvent removed to form 2-chloro-α, α, α-trifluoro-p-tolyl -3- (1-carbamoylethoxy) -4-nitrophenyl ether (2.4 g, 60 °), m.p. 108-111 ° C.

Example 55Z

Preparation of 2-chloro-α, α, α-trifluoro-p-tolyl-3- (3-methyl-1-ethylureido) -4-nitrophenyl ether a) 2-Chloro-α, α, α-trifluoro-β-tolyl -3- (N-ethylchloroformamido) -4-nitrophenyl ether

A mixture of 2-chloro-α, α, α-trifluoro-p-tolyl-3-ethylamino-4-nitro-phenyl ether (3.6 g, 0.01 mol), phosgene (18.9 g, 0.19 mole), 2,6-lutidine (2.2 g, 0.02 mole) and benzene (ΐ30 ml) are heated in a pressure vessel for 64 hours to 90-95 ° C. The mixture is cooled, filtered and the solvent evaporated to give 2-chloro-α, α, α-trifluoro-p-tolyl-3- (N-ethylchloroformamido) -4-nitrophenyl ether.

b) 2-Chloro-α, α, α-trifluoro-p-tolyl-3- (3-methyl-1-ethylureido) -4-nitrophenyl ether

A solution of 2-chloro-α, α, α-trifluoro-p-tolyl-3- (N-ethylchloro-formamido) -4-nitrophenyl ether (4.4 g, 0.01 mole), methylamine (3.3 g , 0.11 mol) and benzene (rv 60 ml) are left for 25 minutes at 0 ° C, then the solution is filtered and the solvent is removed. Benzene (/ v / 100 ml) and hexane (50 ml) are added and the solution washed with water (100 ml) and aqueous 10¾ sodium carbonate solution (2 x 100 ml), dried and the product is absorbed on activated silica gel (rv). 25 g). The product is eluted with a mixture of benzene (400 ml) and methanol (40 ml), the solvents removed and the product recrystallized to form 2-chloro-α, α, α-trifluoro-p-tolyl-3- ( 3-methyl-1-ethylureido) -4-nitrophenyl ether (2.6 g, 62¾), mp 127.5-128.5 ° C.

Example 56

This example shows the herbicidal activity of the subject diphenyl ethers against a variety of common weeds. Using the procedure described below, the ability of diphenyl ethers to control the following weeds was assessed:

At 11.2 kg per acres:

Single-leafed plants Two-leafed plants

Male spore (Echinochloa crus.) Snerle (Convolvulus

Fingeraks (Digitaria spp) arvensis)

Cyperus (Cyperus esculentus) Rippled Junk% g ™ euxs)

Flying Oats (Avena Fatua) Abutilen (Abutilou theophrasis) Agar Mustard (Brassica at 2.2 and 4.5 kg per hectare. Hope) 32 144561

Single-leafed plants

Male Spore (Echinochloa crusgalli) ^ Bermuda grass (Cyanodon dactylon)

Fingerax (Digitaria spp.)

Tag-heron (Bromus tectorum) Fox tail (Setaria faberii)

Durra (Sorghum halepense)

Cyperus (Cyperus esculentus)

Mercury (Agropyron repens) ^ Common ryegrass (Lolium perenne) ^ Flying oats (Avena fatua) ^ Common millet (Panicum miliaceum)

Two-leafed plants

Snerle (Convolvulus arvensis)

Blood Seeds (Xanthium pensyIvanicum) ^ Sesbania (Sesbania macrocarpa) * Rippled Crisp (Rumex crispus) ^ White Flour Goose Foot (Chenopodium album)

Ipomoea (Ipomoea purpurea) ^ Quinoa (Amaranthus retroflexus) fewEnglander (Ambrosia artemisiifolia) * Pile herb (Polygonum pensylvanicum) fr * Tomato (Lycopersicon esculentum)

Abutilon (Abutilon theophrasti) * Wild Carrot (Daucus carota) ^ Agar Mustard (Brassica hopes) - # Only Examples 1-4 ** Tuna Example 5

The following experimental procedure was used - Seeds of selected crops and weeds were planted in soil in trays. For testing the activity of the herbicides before emergence of the plants, the trays are treated with the test compound immediately after planting, and for testing the activity after the emergence of the plants, the seeds were sprouted and after 2 weeks the trays were treated with the test compound. The compound to be tested is dissolved in acetone, diluted with water and sprayed over the trays using a volume of carrier equivalent to ca. 500 liters per liter. ha in the amount of dosage indicated in the tables (kg per hectare, kg / ha). Ca. Two weeks after application of the test compound, the growth status of the plants is noted and the phytotoxic effect of the compound is assessed. Table III indicates the average protection control obtained by the test compounds expressed by the percentage of plants killed by the compounds.

TABLE III

Herbicidal Activity (¾ Protection)

Connection ^ Ear Pan Panels According to plants from ex. Kg / ha emergence_ emergence_: '11,2 4,5,2,2 11,2 4,5 2,2 1 M * 96 82 71 99 75 74 D * 97 52 51 100 74 81 2 M 77 96 96 100 99 92 D 97 100 88 100 92 85 3 M 94 96 100 87 D 95 71 100 77 4 M 87 99 100 94 D 100 83 100 94 5 M 100 86 D 100 99 M * - Single-leafed plants ; D * - Two-leafed plants.

Example 57

This example shows the selective herbicidal activity of the subject diphenyl ethers in a number of agricultural crops. Following the experimental procedure of Example 56, the significant tolerance of the diphenyl ethers in question to some or all subsequent agricultural crops (not all compounds tested against all crops) is assessed: alfalfa, chopped beans, corn, cotton, cucumbers, peanuts, rice, soybeans, tomatoes and wheat (as shown by this tolerance at 50¾ or less eradication of experimental plants at the dosage level, giving more than 50a extinction of many or all of the weeds of Example 56).

The tolerance to cut beans for application before the emergence of plants is shown by the compounds of Examples 1, 2 and 5. The tolerance for maize when applied before the emergence of plants is shown by the compounds of Examples 1 and 2 and by the compounds of Examples 1, 2 and 5 for application after the plants. inception. The compounds of Examples 1, 2 and 5 exhibit tolerance to cotton plants prior to emergence of the plant, and the compound of Example 1 exhibits such tolerance when used after germination and later. Peanut tolerance on application before emergence of plants is shown by the compounds of Examples 1 and 2. Soybean tolerance on application before emergence of plants is shown by the compounds of Examples 1 and 2, and the compound of Example 2 exhibits such tolerance when used before germination and later. The tolerance of rice when used before and after the emergence of plants or when applied to transplanted rice is shown by the compounds of Examples 1 and 2. Tolerance of use before and after the emergence of the plants is shown by the compounds of Examples 1, 2 and 5 relative to wheat.

Example 58

This example shows the herbicidal activity of the subject diphenyl ethers against a number of common weeds. Using the procedure described below, the controlling effect of the diphenyl ethers on subsequent weeds is assessed:

At 11.2 kg per acres:

Single-leafed plants

Male Spore (Echinochloa crusgalli)

Finger Ax (Digitaria spp)

Cyperus (Cyperus esculentus)

Flying Oats (Avena fatua) 35 144561

Two-leafed plants

Snerle (Convolvulus arvensis)

Rumex crispus

Abutilon (Abutilon thophrasti)

Agar mustard (Brassica hopes)

At 2.2 and 4.5 kg per acres:

Single-leafed plants

Male Spore (Echinochloa crusgalli) ^ Bermuda grass (Cynodon dactylon)

Finger Ax (Digitaria spp) ^ Tag-heron (Bromus tectorum) Fox Tail (Setaria faberii)

Durra (Sorghum halepense)

Cyperus (Cyperus esculentus)

Mercury grass (Agropyron repens) ^ Common ryegrass (Lolium perenne) ^ "Flying oats (Avena fatua)

Common millet (Panicum milliaceum)

Two-leafed plants

Snerle (Convolvulus arvensis)

Blood Seeds (Xanthium pensylvanicum) ^ Sesbania (Sesbania macrocarpa)

Rumex crispus ^ White Flour Goose Foot (Chenopodium album)

Ipomoea (Ipomoea purpurea) ^ Kvinoa (Amaranthus retroflexus)

Meadow fir (Ambrosia artemisiifolia) X Pile herb (Polygonum pensylvanicum)

Tomato (Lycopersicon esculentum)

Abutilon (abutilon theophrasti) ^ Wild carrot (Daucus carota) * Age of mustard (Brassica hopes) ^ Examples only 2Z-9Z '^ Examples 1Z and 10Z-55Z only.

36 144561

The following experimental procedure was used. Seeds of selected crops and weeds are planted in soil in trays. To test the activity before the emergence of plants, the trays are treated with the test compound immediately after planting. To test the activity after the emergence of the plants, the seeds are sprouted and after 2 weeks the trays are treated with the test compound. The compound to be evaluated is dissolved in acetone diluted with water and sprayed over the trays using a carrier volume equivalent to ca. 500 liters per liter. ha at the dosage rate (kg per hectare, kg / ha) listed in the tables. Ca. Two weeks after application of the test compound, the growth state of the plants and the phytotoxic effect of the compound is assessed. Table IV sets out the average percentage of protection obtained with the test compounds expressed as the percentage of plants killed by the compounds.

37 144561

TABLE IV

Herbicidal Activity (¾ Protection)

Connection Wha: Before the plants After the plants from ex.-no. -, - emergence emergence 11.2 4.5 2.2 11.2 4.5 2.2 1Z M * 91 100 99 100 D 83 100 100 99 2Z M 97 97 100 99 D 100 80 100 100 3Z M 99 89 184 100 99 +96 D 100 99 J ^ 66 100 100 +97 4Z M 98 80 D 100 100 5Z M 97 84 100 99 D 100 78 100 100 6Z M 65 77 97 91 D 70 55 100 94 7Z M 61 65 65 100 75 82 D 60 57 54 100 77 80 8Z M 81 61 52 85 48 35 D 82 57 46 100 80 66 9Z M 99 90 81 100 97 82 D 92 66 67 100 81 75 10Z M 70 66 67 17 D 100 70 98 85 HZ M 81 88 82 100 D 98 99 99 100 12Z M 86 72 77 99 D 96 93 100 100 13Z M 76 78 77 100 D 90 72 98 100 14Z M 64 30 61 91 D 78 22 94 100 0.3 kg / ha + 0.6 kg / ha 38 144561 TABLE IV [continued) Before the plants After the plants

Connection Ve / ha - emergence emergence from ex no. A / u - - 4.5 2.2 4.5 2 ^ 2_ 15Z M 99 68 79 76 D 100 90 99 94 16Z M 86 67 77 82 D 94 75 96 94 17Z M · 51 20 45 39 D 84 31 89 98 18Z M 67 99 28 28 D 100 100 86 98 19Z M 91 77 84 94 D 96 91 98 97 20Z M 88 80 78 80 D 99 93 88 97 21Z M 91 79 74 90 D 99 90 96 94 22Z M 72 63 60 70 D 98 77 99 100 23Z M 90 55 82 71 D 64 87 100 100 24Z M 91 62 86 84 D 68 97 99 100 25Z M 87 40 97 88 D 88 93 100 100 26Z M 98 75 99 93 D 100 99 100 100 2 7 ZM 76 74 82 99 D 98 90 100 100 28Z M 74 79 73 73 D 95 79 99 100 29Z M 74 66 79 97 D 73 84 100 100 30Z M 81 78 75 91 D 99 94 100 100 31Z M 74 68 61 68 D 99 69 100 100 39 UA5S1 TABLE IV (continued)

Connection Before the plants After the plants from Ex. No. Emergence_ emergence kg / ha: 4.5 2.2 4.5 2.2 32Z M 86 81 86 100 D 100 81 100 100 33Z M 53 79 32 65 D 99 74 98 100 34Z M 35 83 32 47 D 52 85 89 90 35Z M 40 60 45 63 D 40 72 98 80 36Z M 93 100 87 94 D 100 100 100 98 37Z M 99 100 92 100 D 100 100 100 100 38Z M 47 62 43 51 D 86 68 98 58 39Z M 65 77 64 61 D 99 80 98 100 40Z M 86 88 64 81 D 92 98 100 100 41Z M 60 84 71 56 D 96 62 95 94 42Z M 62 83 38 63 D 80 60 98 88 43Z M 0 99 2 61 D 48 100 47 80 44Z M 66 0 6Q 7 D 96 17 98 10 45Z M 13 68 17 53 D 58 77 88 78 46Z M 0 34 00 D 20 87 30 4 47Z M 61 80 11 24 D 40 80 72 84 48Z M 99 100 75 84 D 97 100 100 97 40 144561 TABLE IV (continued)

Connection Before the plants After the plants from ex. emergence_ emergence_ kg / ha: -L5 2.2 4.5 2.2 49Z M 92 100 86 77 D 95 100 100 100 50Z M 90 98 97 100 D 83 100 100 100 51Z M 79 96 75 86 D 100 100 100 98 52Z M 79 98 87 93 67 75 100 100 53Z M 98 98 79 81 D 83 100 100 100 54Z M 83 98 79 71 D 75 98 100 100 55Z M 91 69 31 D 73 95 96 - Single-seeded plants; D = Two-leafed plants Example 59

This example shows the selective herbicidal activity of the subject diphenyl ethers against a number of agricultural crops. Following the general experimental procedure of Example 58, the significant tolerance of the diphenyl ethers to some or all of the following common agricultural crops is assessed (not all compounds tested against all crops): alfalfa, chopped beans, corn, cotton, cucumbers, peanuts, rapeseed, rice, , soybeans, tomatoes and wheat (with tolerance being shown at 50% or less killing of the test compound at dosage levels which gives more than 50% killing of many or all of the weeds of Example 58).

The compounds of Examples 4Z and 26Z show tolerance to cut beans upon application before emergence of plants. Tolerance to maize when applied before the emergence of plants is shown by the compounds of Examples 4Z, 11Z, 19Z, 21Z, 34Z, 40Z, 52Z and 54Z and by application 41 144561 after the plants emergence of the compounds of Examples 1Z, 42, 18Z, 19Z, 21Z, 26Z, 34Z, 36Z, 40Z, 49Z, 52Z, 53Z and 54Z, while tolerance of cotton upon application before the emergence of plants is shown by the compounds of Examples 3Z, 4Z and 30Z, and the compound of Example 3Z also exhibits such tolerance when used after germination and later. Tolerance of peanuts when applied before the emergence of plants is shown by the compounds of Examples 1Z, 3Z, 19Z, 21Z, 30Z, 34Z, 36Z, 40Z, 48Z, 49Z, 50Z, 52Z and 53Z and when applied after the plants emergence of the compounds of Examples 4Z, 18Z, 34Z, 36Z, 37Z, 40Z, 48Z, 53Z and 54Z. Tolerance to rice when used before emergence of plants is shown by the compounds of Examples 4Z, 19Z, 21Z, 30Z, 34Z, 40Z, 52Z and 54Z and when applied after plant emergence or on transplanted rice by the compounds of Examples 3Z, 11Z, 18Z, 20Z, 30Z, 34Z, 40Z, 48Z, 53Z and 54Z. Tolerance to color thistle when used before the emergence of plants is shown by the compound of Example 3Z. Tolerance of soybeans when used before the emergence of plants is shown by the compounds of Examples 3Z, 4Z, 11Z, 18Z, 19Z, 21Z, 26Z, 30Z, 34Z, 40Z, 48Z, 49Z, 50Z, 52Z, 53Z and 54Z, and the compounds of Examples 3Z and 34Z exhibit such tolerance when used after germination and later. Tolerance to wheat when used before the emergence of plants is shown by the compounds of Examples 1Z, 4Z, 18Z, 19Z 26Z, 34Z, 40Z, 50Z and 54Z and when used after plant emergence of the compounds of Examples 4Z, 18Z, 21Z, 30Z, 34Z, 36Z , 48Z and 54Z.

Comparative Example A

In this example, the compound 2-nitro-4-trifluoromethylphenyl-4-chlorophenyl ether (compound B) known from US Patent No. 3,420,892 was compared to the isomeric 2-chloro-4-trifluoromethyl-phenyl-4-nitrophenylether ( compound A) according to the invention, both before and after the emergence and planting of various single- and two-seeded weeds and utility crops. The results are shown in Table V as percentage extinction.

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In this example, Compound B (see Comparative Example A) was compared to a wide variety of compounds of the invention. The results are shown in Table VI as a percentage extinction.

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Claims (2)

52 144561 1. Herbicidal diphenyl ethers, characterized in that they have the general formula: y T xo O r 2 wherein X represents a halogen atom or a cyano group, Y represents a hydrogen atom or a halogen atom, and Z represents hydrogen, a hydroxy group, an alkoxy group, an alkyl group, a halogen atom, an amino group, a cyano group, a carboxy group in free acid or salt form, a carbalkoxy group of up to 4 carbon atoms in the alkoxy moiety, an alkanoyloxy group of up to 4 carbon atoms, an alkyl-substituted carbamoyloxy group of up to 6 the moiety, an alkoxy group substituted by halogen, alkenyl of up to 4 carbon atoms, alkynyl of up to 4 carbon atoms, hydroxy, alkoxy of up to 4 carbon atoms, alkylamino or dialkylamino of up to 4 carbon atoms, carboxy of free acid or salt form, carbalkoxy with up to 4 carbon atoms in the alkoxy moiety, alkanoyl with up to 4 carbon atoms in the alkyl moiety, alkylthio with up to 4 carbon atoms, carbamoyl, alkylcarbamoyl or dialkyl carbamoyl with each up to 4 alkyl carbon atoms, epoxy or alkylsulfonyl with up to 4 carbon atoms, or an amino group substituted with 1 or 2 alkanoyl groups each containing up to 4 carbon atoms, 1 or 2 haloalkanoyl groups each with up to 4 carbon atoms, 1 or 2 alkyl -carbamoyl groups each having up to 4 carbon atoms in the alkyl moiety, 1 or 2 alkylthiocarbonyl groups of the formula -CO-SR, wherein R is alkyl of up to 4 carbon atoms, 1 or 2 alkyl groups having a total of up to 6 carbon atoms, or 1 or 2 hydroxyalkyl groups having a total of up to 6 carbon atoms , or Z represents a morpholino group.