DD151105A5 - HERBICIDE MEDIUM - Google Patents

Abstract

The invention relates to herbicidal compositions containing novel substituted Nitrodiphenylaether of formula I. The novel agents according to the invention are distinguished from agents which contain known nitrodiphenyl ethers in that they have a better herbicidal activity and selectivity and a lower mammalian toxicity.

Description

The invention relates to the preparation of new herbicidal compositions containing novel Nitrodiphenyläther as active ingredients, and methods for controlling weeds.

Characteristic of the known technical solutions

It is known that diphenyl ethers are effective weed control agents (see, for example, U.S. Patent 3,928,416,

3 454 392, 3 798 276, 3 873 303, 4 001 005, 4 046 798,

4 063 929, 4 093 446 and 4 029 493). However, even today, the herbicidal action of a diphenyl ether can not be predicted by its structure alone, as very closely related compounds often show completely different weed control effects (Advances in Agronomy, Vol. 24, pp. 331, 332, 355, 356, 357 and 358 , Herbicides, Chemical Degradation and Mode of Action, Kearney and Kaufman, Volume 2, Dekker, Inc., pp. 552-563 and 728-737 and Mode of Action of Herbicides, Ashton and Crafts as well

U.S. Patents 3,454,392 and 3,776,961).

An ideal herbicide should selectively enable weed control throughout the growing season in a single administration and using small amounts. It should be able to control all conventional weeds by killing them as seeds, as germinating seedlings, as seedlings, and as a growing plant. At the same time, the herbicide should not be substantially phytotoxic to the crops to which it is applied and should not decompose or otherwise spread outdoors to avoid permanent poisoning of the soil. The known diphenyl ether herbicides do not yet meet the ideals.

221980 _7_

Object of the invention

The aim of the invention is to overcome the disadvantages of the known di-, phenylether herbicides, as set forth above, and to produce more selective compounds which complement the activities of the known diphenyl ethers,

Explanation of the essence of the invention

The object of the invention is to provide novel nitrodiphenyl ethers which, in comparison to known nitrodiphenyl ether herbicides, meet each of the following criteria: good herbicidal activity, selectivity and reduced mammalian toxicity.

The invention provides novel herbicides containing as active ingredients a new class of diphenyl ethers of the following structural formula:

CF.

(D

-CH

'WR

QZ

-C ₄ ) -alkyl,

in which

X is hydrogen, halogen, trifluoromethyl, cyano or nitro,

Y is hydrogen, halogen or trifluoromethyl, W is O or S (O) _O , where ρ is 0 to 2, R is (C -, - C ₄ ) -alkyl, phenyl, halogen-substituted phenyl or

Trifluoromethyl-substituted phenyl or phenyl (C ₁ -C ₄ ) -

22 1980

represents alkyl,

C (CH,), where η is O to 4, or (C ₀ -C,) - alkenylene, and

Z CO ₉ R ¹ , CO ₀ H, C0 ~, CONH ₇ , CONHR ¹ , COSR ¹ , CON (R ¹ ) _o , CN, CH ₀ OH, CH ₀ Cl, COR ¹ ,

2 3 1 1

CH ₉ OCH ,, CO ₅ (CR R) CO R or OR represents, in particular

in particular when η is 1, 2, 3, or 4 and R

is (C ₁ -C,) -alkyl, where

1 R (C ₁ -C ₄ ) -alkyl, (C ₃ -C ₆ ) -alkenyl, cyano- (C ₁ -C ₄ ) -alkyl, (C ₃ -C ₆ ) -alkynyl, (C ₃ -C ₄ ) -Haloalkyl, (C ₁ -C ₄ ) -hydroxyalkyl, (C ₁ -C ₄ ) -alkoxy- (C ₁ -C ₄ ) -alkyl, (C ₁ -C ₄ ) -alkoxy- (C ₁ -C ₄ ) -alkoxy- (C ₁ -C ₄ ) -alkyl (ie R ¹ OR ¹¹ OR " ¹ , wherein R" and R " ^{1 represent} . (Cj-C ₄ ) -alkylene and R ^{1 is} (C ₁ -C ₄ ) Alkyl, trifluoroethyl, (C ₃ -C ₄ ) -nitroalkyl, (C ₃ -C ₈ ) -cycloalkyl or phenyl- (C ₁ -C ₄ ) -alkyl (in particular

when Z is CO »R),

3

R and R are the same or different and are selected from hydrogen or methyl, m is 1 to 3, wherein the -CR ² R ³ groups are the same or different when m> 1, and when Z is CO ^ H also the compatible salts of the compounds of the formula I come into question.

By the term "halogen" is meant bromine, chlorine, fluorine or iodine. Preferred halogen substituents are chlorine and fluorine. The terms "alkyl", "alkoxy", "alkenyl" and "alkynyl" refer to all possible straight and branched isomeric forms, so that, for example, "(C ₁ -C ₄ ) -alkyl" denotes any of the groups CH ₃ , C ₃ H ₅ , C ₃ H, C ₄ H ₉ and all isomers of the last two groups.

A narrower class of compounds corresponds to the formula

21-MV1980 * S 97 a 4 _: ..

22 19 80

H - I

II

-CH

'WR

• (CH ₂ ) _n 2

worm

X is hydrogen, halogen, for example bromine, chlorine, fluorine or iodine, trifluoromethyl, alkyl, for example lower alkyl having 1 to 4 carbon atoms, preferably methyl or ethyl, cyano or nitro, in particular chlorine,

Y is hydrogen, halogen, for example bromine, chlorine, fluorine or iodine, or trifluoromethyl, preferably hydrogen,

W is O or S (O) _{r is} preferably 0, S, or SO, and in particular 0,

R is lower alkyl having 1 to 4 carbon atoms, phenyl, phenyl (C.C.sub.1) alkyl, such as benzyl, or phenethyl, where R is preferably methyl or ethyl,

η is 0 to 4, preferably 0,

ρ is 0 to 2, preferably 0 or 1,

Z CO ₂ R ¹ , CO ₂ H, CO ₂ , CONH ₂ , CONHR ¹ , COSR ¹ , CON (R ¹ ) ₂ , CN,

CH ₂ OH, CH ₂ Cl, COR ¹ or CH ₂ OCH ₃ ISt, where R ^{1 is} (C ₁ -C ₄ ) -alkyl or (C ₃ -C ₄ ) -alkenyl, and then, if Z is COOH, the agriculturally acceptable salts of compounds of formula II.

Examples of salts of compounds of formula I and II (if Z is COOH) are the ammonia and amine salts, such as triethylamine. Ethanolamine, the alkali metal and alkaline earth metal salts, such as the salts of Li, K, Na, Ca, Ba, Sr and Mg. The salts are preferably storage stable,

22 1980 -f-

For example, at 18 to 25 ⁰ C, if they are in sealed containers.

A subclass of compounds of Formula II and their salts (which are the subject of U.S. Application Serial No. 50,284, to which the present application is based in part) are those in which X, Y, T7, R, η and ρ are those related and Z is CO ₂ R ¹ , CO ₂ H, C0 ~, CONH ₂ , CONHR ¹ , C0N (R ¹ ) ₂ #CN, CH ₂ OH, CH ₂ Cl or COCH ₃ , where R ^{1 is} (C ₁ -C ₄ ) -alkyl. In this subclass of compounds, it is preferable that X is cyano or chloro, especially the latter, while Y is hydrogen.

An even closer class of compounds corresponds to the formula ·

CF.

III

wherein WR and Z have the meanings given above and X is Cl or CN. Particularly preferred compounds of formula II are those in which X is Cl, WR is OCH ₃ and Z is CO ₃ R, where R is (C ₁ -C ₄ ) alkyl or (C ₃ -C ₄ ) alkenyl ,

Typical compounds of the formula III have the following meanings, ie, WR, X and (CH ₉ ) Z:

19 80

WR

OCH ₃ Cl CO ₂ CH ₃ , OCH ₃ Cl CO ₂ Well, OC ₂ H ₅ Cl CO ₃ CH ₃ , SCH ₃ Cl CO ₂ C ₂ H ₅ , SOCH ₃ Cl CO ₂ C ₂ H ₅ , OCH ₃ Cl CO ₂ C ₂ H ₅ , OCH ₃ Cl C ₂ H ₄ OH,

OC ^ H

OCH

OCH.

SO ₃ CH ₃

Cl Cl

COCH

CO ₂ CH

₆ H ₅ Cl CO ₂ CH ₃ , OCH ₂ CgH ₅ Cl CO ₂ CH ₃ ,

OCH.

OCH.

OCH.

OCH.

OCH.

Cl CO ₂ CH (CH ₃ J ₂ OCH ₃

OCH.

OCH.

OCH.

Cl CO ₂ H, 3 ⁵ 2 ' Cl CON (CH CH ₃ , Cl CH ₂ CO ₂ CH ₃ , CN CH ₂ CO ₂ CO ₃ CH ₃ , Cl CO ₂ CH ₂ O ₂ CH ₃ , Cl cojcll CH = CH ₂ , Cl CO ₂ CH ₂ Cl CN, or CN CO ₃ CH ₃

and similar radicals for Z, in which η is 0.

Of these residues, the following are especially favorable:

WR X (CH ₂ J _n Z WR X (CH ₂ J _n Z OCH ₃ Cl CO ₂ CH ₃ , OCH ₃ Cl CO ₂ CH ₂ CO ₂ CH ₃ , CH ₃ OC ₃ H ₅ Cl CO ₂ CH ₃ , OCH ₃ Cl CO ₂ CHCO ₂ CH ₃ , OCH ₃ Cl CO ₂ C ₂ H ₅ OCH ₃ Cl CO ₂ CH ₂ CH = CH ₂ , OCH ₃ Cl CO ₂ CH (CH ₃ J ₂ OCH ₃ Cl CH ₂ CO ₂ CH ₃ , or OC ₆ H ₅ Cl CO ₂ CH ₃ , OCH ₃ Cl CN

2 2 1 9 0 0 - * -

An even closer class of compounds according to the present invention corresponds to the formula

EV

wherein R is (C 1 -C 4) -alkyl, for example methyl, ethyl, n-propyl, isopropyl, η-butyl, sec-butyl or tert-butyl, and n * and m ^{1 are} O or 1. These compounds show a particularly good herbicidal activity and have a low toxicity to animals, in particular a low hematological toxicity.

The diphenyl ethers of the formula I are suitable as pre-emergence and post-emergence herbicides. Pre-emergence herbicides are commonly used to treat the soil by application either before sowing, during sowing or after sowing the crop seeds, and before crop emergence.

Post-emergence herbicides are those that are applied after the crops have grown out of the ground and are in their growing season. The compounds of the invention are particularly active herbicides as Nachauf run.

The invention therefore provides a means of controlling weeds, usually on fields where crops grow, by operating on the growing weeds, for example weed seedlings, or on the surface of a crop. Growth medium before emergence of the weeds one or more of the diphenyl ether in amounts

2 2 19 8 0 _ * _

which are sufficient to combat the growth of the weeds.

When used to control weeds growing between transplanted rice plants, the aethers may be used during either the pre-emergence or post-emergence stages of the weeds, i. H. they can be applied to the transplanted rice plants as well as their growth medium either before the weed plants emerge or during the early stages of growth of the weeds. The ethers can be applied to the growth medium either before or after transplanting the rice to this medium.

The diphenyl ethers can be used in any amount that causes the required control of the weeds. A standard amount with which the diphenyl ethers according to the invention are applied is between 0.0056 and 5.6 kg / ha. A preferred range varies between 0.01 and 1.2 kg / ha. The diphenyl ethers are particularly effective as post-emergence herbicides for controlling weeds growing between crops soybeans, peanuts, cotton, safflower, oilseed rape, beet sugar and small crop crops such as wheat, barley, oats and rice, these being applied in extremely small amounts can.

Under certain conditions, the diphenyl ethers can be advantageously incorporated into the soil or other growth medium prior to planting a crop, which can be conventionally done, for example, simply by mixing with the soil by applying the diphenyl ether to the soil surface and then pouring it into the soil at the desired depth or using a liquid carrier.

221980

When used as herbicides, one or more of the compound (s) of Formula I of the invention are usually used in conjunction with an agriculturally acceptable carrier or diluent (and optionally with a surfactant) using herbicidal formulations containing in general from 0.1 to 95 and in particular from 1 to 95 and most preferably from 5 to 95% by weight of the active herbicidal component which consists of one or more of the diphenyl ethers of the formula I. These herbicidal preparations may be in the form of ready-to-use dusts, solutions, emulsions, suspensions, granules or pellets. Optionally they may be employed in the form of concentrated solutions, wettable powders, water dispersible granules, emulsifiable concentrates, flowable liquid suspensions, flowable emulsion concentrates, pastes or dust concentrates, if necessary with further liquid (usually water) or finely divided solids to produce dilute solutions , Suspensions, emulsions or dusts, which can then be used directly as herbicidal preparations.

By "agriculturally acceptable carrier or diluent" is meant a substance which can be used to dissolve, disperse, disperse, or otherwise dilute the active ingredient without affecting its efficacy, and further, without permanent damage The sites of application takes place, such as the soil, the device used and the crops.

It is usually convenient, especially in the case of postemergence treatment, to add adjuncts such as wetting agents, spreading promoters, dispersants, tackifiers, adhesives or the like. Examples of adjuvants used in a conventional manner

2 2 1 9 8 O - ίο - -

can be found in the publication "Detergents and Emulsifiers 1969 Annual" by John W. McCutcheon, Inc.

Examples of solvents which are suitable for carrying out the invention are alcohols, ketones, aromatic hydrocarbons, dimethylformamide, dioxane and dimethyl sulfoxide. Mixtures of these solvents can also be used. The concentration of the solution may vary from about 2 to about 98 weight percent of the diphenyl ether (s), with a preferred range of from about 25 to about 75 percent.

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 mixtures of these solvents, together with a Emulsifying agent that allows dispersion in water. Suitable emulsifiers are, for example, ethylene oxide derivatives of alkylphenols or long-chain alcohols, mercaptans, carboxylic acids and reactive amines and partially esterified polyhydric alcohols. Solvent-soluble sulfates or sulfonates, such as alkaline earth salts or amine salts of alkylbenzenesulfonates, and the fatty alcohol sodium sulfates having surfactant properties can be used as emulsifying agents, either alone or in combination with an ethylene oxide reaction product. Flowable emulsion concentrates are formulated similarly to the emulsifiable concentrates and contain, in addition to the above components, water and a stabilizer such as a water-soluble cellulose derivative or a water-soluble salt of a polyacrylic acid. The concentration of the active ingredient in the emulsifiable concentrates is usually between 10 and 60 wt .-% and is in flowable emulsion concentrates up to 75 wt .-%.

221980

Wettable powders suitable for spraying may be prepared by mixing the compound with a finely divided solid such as a clay, inorganic silicates and carbonates, and silica, and incorporating wetting agents, tackifiers, and / or dispersants. The concentration of the active ingredients in such formulations is typically between about 20 and about 98 weight percent, and preferably between about 40 and about 75 weight percent. A dispersant may be employed in an amount of from about 0.5 to about 3 percent by weight of the composition and a wetting agent in an amount of from about 0.1 to about 5 percent by weight of the composition ,

Dusts can be prepared by mixing the compounds of the invention with finely divided inert solids, which may be organic or inorganic in nature. Materials suitable for these purposes include botanical flours, silicas, silicates, carbonates and clays. A suitable method of producing a dust is to dilute a wettable powder with a finely divided carrier. Dust concentrates containing from about 20 to about 80% by weight of the active ingredient are usually made and subsequently diluted to concentrations of about 1 to about 10% by weight.

Granular formulations may be prepared by impregnating a solid such as a granular Fuller ¹ S earth Vermikulith, vermählender corn residues, Saathülsen such as bran and other cereal husks, or similar material. A solution of one or more of the diphenyl ethers in a volatile organic solvent may be sprayed or mixed with the granular solid, after which the solvent is removed by evaporation. The granular material may be of any suitable size. A preferred size is between 0.25 and 1.25 mm, the material typically containing from about 2 to about 15% by weight of the active ingredient.

2.2 19 80. - »-

The diphenyl ethers of the present invention may further be treated with fertilizers or fertilizer materials prior to their entry. be mixed. One type of solid fertilizer preparation in which the diphenyl ethers can be used consists of particles of a fertilizer or fertilizers, such as ammonium sulfate, ammonium nitrate or ammonium phosphate, which particles may be coated with one or more of the ethers. The solid diphenyl ethers as well as solid fertilizing materials may further be mixed together in blending equipment, and may also be incorporated into fertilizers which are in granular form. Any ratio of the diphenyl ether to the fertilizer can be maintained which is suitable for the crops and the weeds to be treated. The diphenyl ether is usually present in an amount of from about 5 to about 25 percent by weight of the fertilizer formulation. These preparations are fertilizers which favor the rapid growth of the desired plants while controlling the growth of undesirable plants.

The diphenyl ethers according to the present invention can be applied as herbicidal sprays by known methods, for example as high volume conventional hydraulic sprays, low volume sprays, air blowing sprays, air sprays and dusts. In a low volume application, usually a solution of the compound is used. The dilution and the amount applied usually depend on various factors, for example, the type of apparatus used, the method of application, the area to be treated, and the type and stage of development of the weeds.

For some applications it may be convenient to use the diphenyl ether of formula I in conjunction (usually in admixture) with other herbicides, as described, for example, in THE Pesticide Manual, The British Crop Pro.

2 2 19 8 0 - «-

tection Council, 6th edition, 1979) and Australian Patent 506,509.

The following examples illustrate the invention. The percentages are by weight unless otherwise indicated.

embodiments example 1 Preparation of methyl 2-inethoxy-2- / 2-nitro-5- (2-chloro-4-

trilfuormethylphenoxy) phenoxy7acetat

9 g of the potassium salt of 2-chloro-4-trifluoromethyl-73 '-hydroxy-4'-nitrodiphenyl ether (with respect to the preparation, see US Pat. No. 4,093,446) in dimethyl sulfoxide is mixed with 4.3 g (cf., Gross and 99, 3260 _y (1966)), methyl CX-chloro- (Χ-methoxyacetate) reacted at room temperature, the color changes rapidly from orange-red to pale yellow, the reaction mixture is taken up in ether and washed several times with an aqueous 0.05% sodium hydroxide solution and then washed with water, dried, filtered through activated silica gel and then the solvent is removed, whereby the desired A'ther is obtained in the form of an oil in an amount of 5.4 g on standing, the product is obtained, which melts at 59 to 60 ⁰ C.

Elemental analysis:

found: C 46.79; H, 2.87; N 3.73; Cl 8.30; F 13.01

requires: C 46.86; H 3.01; N, 3.21; Cl 8,14; F 13.08

2 2 1.9 8

This compound corresponds to the formula

-CH

'OCH

 CO CH

Another designation is methyl -V-methoxy-CX - / - (2-nitro-5- (2-chloro-4-trifluoromethylphenoxy) phenoxy / -acetate or 2-chloro-4-trifluoromethyl-3 '- (T-methoxy 1-methoxycarbonylm.ethoxy) -4'-nitrodiphenyl ether.

Example 2 Preparation of 2-chloro-4-trifluoromethyl-3 '- (1-methoxy-1-one

carboxymethoxy) -4'-nitrodiphenyläther

10 g of 2-chloro-4-trifluoromethyl-3 '- (1-methoxy-i-methoxycarbonylinechoxy) -4'-nitrodiphenyl ether are dissolved in methanol / water (100 ml / 9 ml), whereupon the solution is cooled to 10 ⁰ C in a Is cooled ice bath. A solution of 3.5 g of aqueous 50% NaOH in 25 ml of methanol is added and the mixture is stirred for 5 minutes. The reaction mixture is poured onto ice, extracted with ether and the ether discarded. The aqueous phase is neutralized with an aqueous 5% H ₃ SO ₄ (88 ml), extracted with methylene chloride, and the extract is dried and stripped to give 2-chloro-4-trifluoromethyl-3 '_ {1-methoxy-1 carboxymethoxy) -4'-nitrodiphenyl ether in an amount of 9.2 g (95%). H NMR of the 3 'side chain ^ (CDCl,.) 5.6 (s, 1H), 3.6 (s, 3H).

AS

2 2 19 8 0 - ^w -

The free acid prepared in the manner described above disproportionates slowly at room temperature (18 to 25 ⁰ C), while its sodium salt disproportionates within 24 hours. The sodium salt is prepared by reaction in solution between the free acid and sodium hydroxide.

Example 3 Preparation of 2-chloro-4-trifluoromethyl-3 '- (i-methoxy-1-)

äthoxycarbonylmethoxy) -4'-nitrodiphenyläther

5 g of 2-chloro-4-trifluoromethyl-3 '- (1-methoxy-1-methoxycarbonylmethoxy) -4'-nitrodiphenyl ether are dissolved in 50 ml of ethanol. Separately, 0.1 g of NaH is dissolved in 5 ml of ethanol. The two solutions are combined and at 63 ⁰ C for 3 hours erhitzt..Die reaction mixture with ether / hexane (50 / 5O ₇ based on the volume) and washed the organic phase with water, dried, filtered through neutral alumina, and stripped wherein 2-chloro-4-trifluoromethyl-3 '- (1-methoxy-1-ethoxycarbonylmethoxy) -4'-nitrodiphenyl ether is obtained in an amount of 1.1 g (yield 21%). ¹ H NMR of the 3 'side chain ^ f (CDCl ₃ ) 5.6 (s, 1H), 4.3 (quart, 2H), 3.6 (s _# 3H), 1.3 (t, 3H) ,

Example 4 . ,

Preparation of 2-chloro-4-trifluoromethyl-3 '- (1-methoxy-1-isopropoxycarbonylmethoxy) -4'-nitrodiphenyl ether

5 g of 2-chloro-4-trifluoromethyl-3 '- (1-methoxy-1-methoxycarbonylmethoxy) -4'-nitrodiphenyl ether are dissolved in 10 ml of isopropanol and heated to 65 ° C with stirring. 0.5 g of NaH are dissolved in isopropanol and added in aliquots of the above solution until the reaction is complete. The reaction mixture is diluted with ether and the ether phase is washed with water, dried, filtered through paper and dried.

22 19 80 - »-

stripping ", wherein the desired product is obtained in an amount of 0.8 g (15%). H NMR of the 3'-side chain ^ _(CDCl3) 5.4 (s, 1H), 5.0 (sept., 1H ) 3,5 (s, 3H) ₇ 1,1 (d, 6H).

Example 5 Preparation of 2-chloro-4-trifluoromethyl-3 '- (1-methoxy-1-one

allyloxycarbonylmethoxy) -4'-nitrodiphenyläther

5 g of 2-chloro-4-trifluoromethyl-3 '- (1-methoxy-1-methoxycarbonylmethoxy) -4'-nitrodiphenyl ether are dissolved in 50 ml of allyl alcohol and meshed with 0.3 g of NaH, predissolved in 10 ml of allyl alcohol. The reaction mixture is stirred at room temperature overnight, then diluted with ether / hexane (50/50 by volume) and the organic phase washed with water, dried and filtered through activated alumina and then stripped to give 2-chloro-4 trifluoromethyl-3 '- (1-methoxy-1-allyloxycarbonylmethoxy) -4'-nitrodiphenyl ether (1.9 g, 36%) is obtained. P ^ ¹ H NMR of the 3'-side chain. _(CDCl3) 5.5 (s, 1H), 5.1 to 6.1 (m, 3H), 4.7 (d, 2H), 3.7 ( s, 3H).

Example 6 Preparation of 2-chloro-4-trifluoromethyl-3 '- (i-ethoxy-j-

äthoxycarbonylmethoxy) -4'-nitrodiphenyläther

1 equivalent of 2-chloro-4-trifluoromethyl-3'-hydroxy-4'-nitrodiphenyl ether is dissolved in methyl ethyl ketone. An excess of the equivalent amount of anhydrous potassium carbonate is added. The reaction mixture is heated under reflux with stirring for 15 to 30 minutes to form the potassium salt and then cooled to room temperature. 1 equivalent of ethyl (X-chloro-Q-ethoxyacetate, prepared according to Ber 44: 3213, Comp Rend 152: 960) is added and the mixture is stirred for 15 to 30 minutes The reaction mixture is treated with ether or ether / Hexane (50/50,

22 19 80 -Z-

by volume) and the extract washed with water, dried and filtered through activated alumina and then stripped to give 2-chloro-4-trifluoromethyl-3 '- (1-ethoxy-1-ethoxycarbonylmethoxy) -4'-nitrodiphenyl ether becomes. H NMR of the 3 'side chain (T (CDCl ₃₎ 5.6 (s, 1H), 4.2 (quart. 2H), 3.8 (quart. 2H), 1.2 (2t, 6H).

Example 7 Preparation of 2-chloro-4-trifluoromethyl-3 '- (1-benzyloxy-

} 1-methoxycarbonylmethoxy -4'-nitrodiphenyläther

2.3 g of 2-chloro-4-trifluoromethyl-3 '- (1-benzyloxy-1-benzyloxycarbonylmethoxy) -4'-nitrodiphenyl ether are dissolved in 25 ml of methanol and combined with a solution of 0.05 g of NaH in methanol. The reaction mixture is stirred at room temperature for 3 hours, then diluted with ether, then the ether layer washed with water, dried and filtered through alumina and stripped to give 2-chloro-4-trifluoromethyl-3 '- (1-benzyloxy-1-methoxycarbonylmethoxy ) -4'-nitrodiphenyl ether is obtained in an amount of 0.5 g (25%). ¹ H NMR S (COCl ₃ ) 6.5-8.0 (m, 11H), 5.6 (s, 1H), 4.8 (s, 2H) 3.7 (s, 3H).

Example 8

Preparation of 2-chloro-4-trifluoromethyl-3 '- (1-benzyloxy- .

) 1-benzyloxycarbonylmethoxy -4'-nitrodiphenyläther

10 g of methyl OC, CX dimethoxyacetate, 24.3 g benzyl alcohol and 0 # 1 9 p-toluenesulfonic acid are combined and heated to 130 ⁰ C with stirring for about 12 hours. Since various products are present, the reaction sample is purified by preparative liquid chromatography to yield 5.1 g of the pure product. Benzyl OC benzyloxy-OC-methoxyacetate is then chlorinated (Ber. 44: 3213, MyIO), said Benzylbenyloxychloracetat is obtained. This reagent

2 2 19 8 0 -S-

is used for the alkylation of the potassium salt of 2-chloro-4-trifluoromethyl-3'-hydroxy-4'-nitrodiphenyl ether using the method described in Example 6, wherein 2-chloro-4-trifluoromethyl-3 ¹ - (1-benzyloxy-1 -benzyloxycarbonylmethoxy) -4'-nitrodiphenyl ether. ¹ H NMR cf _(CDCl3) 6.3 7.9 (m, 16H) 5.6 (s, 1H), 5.1 (s, 2H), 4.7 (s, 2H).

Example 9

Preparation of 2-chloro-4-trifluoromethyl-3 '- (1-methylthio-1- ethoxycarbonylmethoxy) -4'-nitrodiphenyl ether

Methyl (X-chloro (X- methylthioacetate) is synthesized by the method of Weygard and Bestman (Ber 89: 1912 (1956)) which is then used to alkylate the potassium salt of 2-chloro-4-trifluoromethyl-3 '. hydroxy-4'-nitrodiphenyl ether according to the method described in Example 6, to give 2-chloro-4-trifluoromethyl-3 '- (1-methylthio-1-ethoxy-carbonylmethoxy) -4'-nitrodiphenyl ether 3 ¹ side chain (/ (CDCl ₃ ) 5.5 (s, 1H), 4.2 (quart, 2H), 2.2 (S ₇ 3H), 1.3 (t, 3H).

Example 10 Preparation of 2-chloro-4-trifluoromethyl-3 '- (1-methylsulfinyl)

1-äthoxycarbonylmethoxy) -4'-nitrodiphenyläther

1 g of 2-chloro-4-trifluoromethyl-3 ¹ - (1-methylthio-1-ethoxycarbonylmethoxy) -4'-nitrodiphenyl ether is dissolved in 3 0 ml of methylene chloride and cooled to 1 ⁰ C with stirring in an ice bath. Separately, 0.35 g of m-chloroperoxybenzoic acid (85% purity) is dissolved in 2 ml of methylene chloride and also cooled to 1 ° C. The peroxide solution is then added dropwise to the diphenyl ether solution and after the addition is complete, the reaction mixture is warmed to room temperature The methylene chloride solution is washed with an aqueous 5% Na ₃ SO 4 solution and then with water, dried, filtered through aluminum oxide and stripped to give 2-chloro-4-tri

2 2 19 8 0 - »-

fluoromethyl-3 '- (1-methylsulfinyl-1-ethoxycarbonylmethoxy) -4'-nitrodiphenyl ether in an amount of 0.1 g. ¹ H NMR of the 3 'side chain / (CDCl ₃ ) 5.3 (s, 1H), 4.3 (quart, 2H), 2.7 (s, 3H), 1.2 (t, 3H).

Example 11 .

Preparation of 2-chloro-4-trifluoromethyl-3 '- (1-methylsulfonyl-

"1-ethoxycarbonylmethoxy) -4-nitrodiphenyl ether

1 _f 4 g of 2-chloro-4-trifluoromethyl-3 '- (1-methylthio-i-ethoxycarbonylmethoxy) -4'-nitrodiphenyl ether are dissolved in 50 ml of methylene chloride and heated to reflux. Separately, 0.7 m-chloroperoxybenzoic acid is dissolved in 2 ml of methylene chloride and added in aliquots of the above-mentioned solution until the reaction is completed. The reaction mixture is washed with water, dried and filtered through paper a few times and then stripped to give 2-chloro-4-trifluoromethyl-3 '- (1-methylsulfonyl-i-ethoxycarbonylmethoxy) -4'-nitrodiphenyl ether in an amount of 1, 3 g is obtained. ¹ H NMR of the 3 'side chain (/ (CDCl ₃ ) 5.4 (s, 1H), 4.3 (quart, 2H), 3.2 Cs, 3H), 1.3 (f, 3H).

Example 12

Preparation of 2-chloro-4-trifluoromethyl-3 '- (1-methoxy-1-cyanomethoxy) -4'-nitrodiphenyl ether

25 g of C (methoxyacetonitrile are dissolved in 80 ml of carbon tetrachloride To this solution are added 21.4 g of N-bromosuccinimide and 3.7 g of azobisisobutyronitrile The reaction mixture is heated to reflux for a total of 10 hours to give at least 50% conversion The carbon tetrachloride is stripped off and the residue is distilled off The product is distilled at 29 to 33 ° C. and under a pressure of 1 mm, giving 16.4 g of CC-bromo-ethylmethoxyacetonitrile, which becomes alkyl -

2219'8 Ο * - * "

tion of the potassium salt of 2-chloro-4-trifluoromethyl-3'-hydroxy.-xy-4'-nitrodiphenyl ether according to the method described in Example 6, wherein 2-chloro-4-trifluoromethyl-3 ¹ (1-methoxy- 1-cyanomethoxy) -4'-nitrodiphenyl ether. ¹ H NMR of 3 'side chain C ^ (CDCl ₃ ) 5.9 (s, 1H), 3.7 (s, 3H).

Example 13 Preparation of 2-chloro-4-trifluoromethyl-3 '- (1-phenoxy-1-)

cyanomethoxy) -4'-nitrodiphenyläther

3.4 g of Q (-Phenoxyacetonitrile, 5.6 g of N-bromosuccinamide, 0.56 g of azobisisobutyronitrile and 30 ml of carbon tetrachloride are combined and heated to reflux with stirring - A General Electric height sun is directed onto the reaction vessel The reaction mixture is dissolved in hexane, washed with water and dissolved with anhydrous Na 2 SO 4, filtered through silica gel and stripped to give {X-phenoxy-0 (-bromoacetonitrile in an amount of 1.1 g This material is used to alkylate the potassium salt of 2-chloro-4-trifluoromethyl-3'-hydroxy-4'-nitrodiphenyl ether according to the method described in Example 6 to give 2-chloro-4-trifluoromethyl-3 '- (1 ¹ H NMR of the 3 · side chain ^ (CDCl ₃ ) 6.7 to 8.1 (m, 11H), 6.5 (s, 1H).

Example 14

Preparation of 2-chloro-4-trifluoromethyl-3 '- (1-methoxy-1-one

dimethylaminocarbonylmethoxy) -4'-nitrodiphenyläther

Dimethylamine gas is bubbled through 27 g of methyl OC (X-dimethoxyacetate containing 1 g of sodium methylate for 3.5 hours.) The reaction mixture is then filtered through paper and stripped to give Ν, Ν-dimethyl- (X, (X ) dimethoxy-

2 2 19 8 0 ™

acetamide is obtained in an amount of 24.9 g. This compound is then combined with acetyl chloride in an amount of 13.3 g and heated to 60 ⁰ C with stirring for about 4 hours. The reaction mixture is then filtered through paper and stripped to give 24.4 g of N, N-dimethyl- (X-chloro- (X-methoxyacetamide) This material is used to alkylate the potassium salt of 2-chloro-4-trifluoromethyl-3 '-hydroxy-4'-nitrodiphenyläther used according to the method described in example 6 to give 2-chloro-4-trifluoromethyl-3 ¹ - (1-methoxy-1-dimethylaminocarbonylmethoxy) is -4'-nitrodiphenyläther obtained ¹ H NMR of the. 3'-side chain Cf _(CDCl3) 5.5 (s, 1H), 3.5 (s, 3H), 3.1 (s, 3H), 2.9 (s, 3H).

Example 15 Preparation of 2-chloro-4-trifluoromethyl-3 '- (1-methoxy-1-one)

acetylmethoxy) -4'-nitrodiphenyläther

10 g of methylglyoxal dimethyl acetal, 6.7 g of acetyl chloride and 100 mg of benzyltriethylammonium chloride are heated at reflux for about 4 hours. The reaction mixture is then stripped and distilled to give 1-chloro-1-methoxy-2-oxopropan is obtained in an amount of 7.6 g which was distilled at 70 ⁰ C under a pressure of 65 mmHg. This material is then used for the alkylation of the potassium salt of 2-chloro-4-trifluoromethyl-3'-hydroxy-4'-nitrodiphe.nyläther according to the method described in Example 6, wherein 2-chloro-4-trifluoromethyl-3 '- ( 1-methoxy-1-acetylmethoxy) -4'-nitrodiphenyl ether. H NMR of the 3 'side chain (/ (CDCl ₃₎ 5.3 (s, 1H), 3.5 (s, 3H), 2.4 (s, 3H).

22 19 8

Example 16 Preparation of 2-chloro-4-trifluoromethyl-3 '- (1,2-dimethoxy)

oxyäthoxy) -4'-nitrodiphenyläther

10 g of methoxyacetaldehyde dimethyl acetal, 6.3 g of acetyl chloride and 10 mg of benzyltriethylammonium chloride are combined and heated to reflux for 1 hour. The reaction mixture is stripped and then distilled. 3.8 g of 2-chloro-1,1-dimethoxyethane distill at 62 ⁰ C under a pressure of 80 mmHg. This material is used to alkylate the potassium salt of 2-chloro-4-trifluoromethyl-3'-hydroxy-4'-nitrodiphenyl ether by the method described in Example 6 to give 2-chloro-4-trifluoromethyl-3 '- (1,2 -dimethoxy ethoxy) -4'-nitrodiphenyl ether. ¹ H NMR of 3 'side chain (/' (CDCl ₃ ) 5.4 (t, IHO), 3.7 (d, 2H), 3.4 (s, 3H), 3.3 (s, 3H) ,

Example 17 Preparation of 2-chloro-4-trifluoromethyl-3 '- (1-methoxy-3-)

methoxycarbonylpropoxy) -4'-nitrodiphenyläther

Methyl 4-oxo-n-butyrate is synthesized from 4.9 g of monomethyl succinate according to the method described in "Sym 767 (1976)". The methyl 4-oxo-n-butyrate is then dissolved in methanol with stirring for about 1 hour to give methyl 4,4-dimethoxy-n-butyrate. The methanol is then stripped of the reaction and the remainder distilled. Thereby distils 4,4-dimethoxy-n-butyrate at 112 ° C under a pressure of 70 mmHg in an amount of 15.7 g simultaneously with an impurity.

15.7 g of methyl 4,4-dimethoxy-n-butyrate, 10 g of acetyl chloride and 100 mg of copper bronze are combined and heated under reflux for 2 hours. The reaction mixture is filtered through paper and stripped to give 13.2 g of methyl 4-chloro-4-methoxy-n-butyrate plus impurities. This material is used for the alkylation of the potassium salt of

2 2 19 8 0

Used 2-chloro-4-trifluoromethyl-3'-hydroxy-4'-nitrodiphenyl ether according to the method described in Example 6, whereby 2-chloro-4-trifluoromethyl-3 ¹ - (i-methoxy-3-methoxycarbonylpropoxy) -4 ' -nitrodiphenyl ether is obtained. ¹ H NMR of the 3'-side chain <f _(CDCl3) 5.4 (t, 1H), 3.7 (s, 3H), 3.4 (s, 3H), 2.1 to 2.7 (m , 4H).

Example 18

Preparation of 2-chloro-4-trifluoromethyl-3 '- / i-methoxy-T- (methoxycarbonylmethoxycarbonyl) methoxy / 4'-nitrodiphenyl ether

10 g of methyl Oi, CX-dimethoxyacetate, 3 g of powdered NaOH and 50 ml of methanol are combined and heated to reflux for 20 hours. The methanol is stripped to yield sodium (X, Oi -dimethoxyacetate.

7.7 g of sodium (X, Qf-dimethoxyacetate, 8.3 g of C 1 -bromoacetate, 25 ml of methyl ethyl ketone, 2 00 mg of benzyltriethylammonium bromide and 0.5 g of sodium iodide are combined and heated to reflux for 2 0 hours Ether, filtered through paper and collected to give 8.9 g of methoxycarbonylmethylQf, $ -dimethoxyacetate, this compound is dissolved in methoxycarbonylmethyl-CT-chloro- (X-methoxyacetate according to the method of MyIo (loc. Cit .: Ber This material is then used to alkylate the potassium salt of 2-chloro-4-trifluoromethyl-3-hydroxy-4'-nitrodiphenyl ether according to the procedure described in Example 6 to give 2-chloro-4-trifluoromethyl 3 ' ~ // \ -methoxy-1- (methoxycarbonylmethoxycarbonyl) methoxy.7-4 ¹ -nitrodiphenyl ether H NMR of the 3 ¹ -side CT (CDCl ₃ ) 5,6 (s, 1H), 4,6 (s, 2H), 3.6 (s, 3H), 3.5 (S, 3H).

2 2 19 8

Example 19 Preparation of 2-chloro-4-trifluoromethyl-3 '- / Ί-methoxy-1 -

(methoxycarbonylethoxycarbonyl) methoxy7 ~ 4'-nitrodipheny1-

ether

9.6 g of sodium, (X-dimethoxyacetate, 11.3 g of methyl (X- bromopropionate), 60 ml of methyl ethyl ketone, 200 mg of benzyltrimethylammonium bromide and 0.5 g of sodium iodide are combined and heated to reflux for 2 days diluted with ether, filtered through paper and stripped to give (1-methoxycarbonylethyl) dimethoxyacetate in an amount of 11.2 g.

(1-Methoxycarbonylethyl) chloromethoxyacetate is synthesized from (1-methoxycarbonylethyl) dimethoxyacetate according to the method described in "Ber." 44: 3213 of MyIo. This material is used for the alkylation of 2-chloro-4-trifluoromethyl-3'-hydroxy-4'-nitrodiphenyl ether according to the method described in Example 6, wherein 2-chloro-4-trifluoromethyl-3 '- / 1-methoxy-1 - (1-methoxycarbonyläthoxycarbonyl) methoxy / 4'-nitrodiphenyl ether, ¹ H NMR of the 3 'side chain

</ \ cDCl ₃ ) 5.6 (s, 1H), 5.1 (quart, 1H), 3.7 (s, 3H), 3.6 (s, 3H), 1.5 (d, 3H ).

The -OCH (WR) QZ group (see formula I) of the compounds of the preceding examples can be represented as follows:

• iq TSS

Ρ axp a ^ xeds θ ^ υτχ axp x 'uaqassassui? 6 I sxq L axaxdsxaa Jiap uassunpuxqjSA 3

uaqosTXHjf-rsÄqd sxp puxs ı axxaqej, uepuaßxoj aap

anj q «j pun oadosi jng: aa-τ 'xAq ^ jnj ^ a' xEq ^ ew anj aw sstsm

ut. usqaq.s ßunxxaqsuetuuipsnz uapuaqa ^ sjcoA asp

SW ³ OO (SW) HO ³ OO (3K0) HOO 3W ³ OO ³ HO ³ OO (SKO) HOO 3W ³ OO ³ HO ³ HO (SKO) HOO 3KO ³ HO (3KO) HOO 3K00 (3KO) HOO ³ SWNOO ( SKo) HOO N3 (qaO) H3O NO (SKO) HOO 33 ³ OO (SW ³ OS) HOO 33 ³ OO (3WOS) HOO 33 ³ OO (SKS) HOO qd ³ HO ³ OO (qd ³ H00) HOO 3W ³ OO (qd ³ H00) HOO 33 ³ OO (330) HOO H 2 HO = H 2 O ³ HO ³ OO (SKO) HOO Jd-T ³ OO (SWO) HOO 33 ³ OO (3K0) HOO H ³ OO (SKO) HOO SW ³ OO (SWO) HOO

6X QX LX 9X 'SX

 εχ

'ZX

'XX

'OX

* 6

'8th

'L

* 9

• ε

'Z

• χ

8 6 I ZZ

Table I Diphenyl ether - Physical data

^C (require ^H (require N (require ei (require

Found formula (found) derlich) found derlich) found derlich)

1 59-60 ⁰ C 2 oil 3 oil 4 oil 5 oil 6 oil 7 oil 8th oil 9 oil 10 oil 11 oil 12 oil 13 oil 14 oil 15 oil 16 oil 17 oil 18 ' oil 19 oil

46.79 (46.86) 2.87 (3.01) 3.73 (3.21) 8.30 (8.14) fs3

42.24 (45.46) 2.67 (2.62) 3.29 (3.31) 12.52 (13.72) ^

48.67 (47.96) 3.43 (3.35) 3.07 (3.11) 7.79 (7.87) J ^

C ₁₉ H ₁₇ ClF ₃ NO ₇ 49.92 (49.10) 3.69 (3.69) 2.75 (3.01) 7.39 (7.63) CO

C ₁₉ II ₁₅ ClF ₃ NO ₇ -50.33 (49.31) 3.41 (3.27) 2.92 (.3.02) 7.57 (7.66) ©

C ₁₉ H ₁₇ ClF ₃ NO ₇ 47.69. (49.21) 3.94 (3.69) 3.20 (3.02) 9.66 (7.64)

Obtained as a 50% mixture with benzyl alcohol

Structure proof by NiVIR (see Example 7)

C ₂₉ H ₂₁ ClF ₃ NO ₇ 58.70 (59.14) 3.63 (3.59) 2.74 (2.38) 6.46 (6.02)

C ₁₈ H ₁₅ ClF ₃ NO ₅ S 44.31 (46.41) 3.13 (3.25) 2.91 (3.01) 8.16 (7.61)

C ₁₀ H ₁₁ -ClF-NO-S 44.07 (44.87). 3.23 (3.14) 2.74 (2.91) · -

C ₁₈ H ₁₅ ClF ₃ NO ₈ S 43.45 (43.43) 2.98 (3.04) 2.60 (2.81) 9.59 (7.12)

C ₁ H _1n ClF-N ₀ O ₁ . 48.50 (47.72) 2.93 (2.50) 7.22 (6.96) 8.36 (8.80)

^C 21 ^H 12 ^C1F 3 ^N 2 ° 5 ⁵³ x ⁹⁴ ( ⁵⁴ x ²⁷ x ² x ⁶⁰ ( ² x ⁶⁰ ) ⁶ x ³³ ( ⁶ x ⁰³ ) ⁷ x ⁷⁰ ( ⁷ x ⁶³ )

C ₀ H ^ ClF ₀ N ₀ O ,. 48.15 (48.17) 3.57 (3.59) 6.62 (6.24) 7.78 (7.90) Io JLo JZb

48.55 (48.53) 3.16 (3.11) .3.62 (3.33) 8.38 (8.43)

48.23 (48.30) 3.58 (3.58) 3.59 (3.31) 8.18 (8.39)

48.91 (49.21) 3.97 (3.69) 2.51 (3.02) 7.75 (7.64)

45.99 (46.12) 3.26 (3.06) 2.92 (2.83) 7.47 (7.17)

47.34 (47.31) 3.40 (3.37) 3.59 (2.76) 7.41 (6.98)

22 19 80

Typical examples of other compounds according to the present invention of the formula I are the following:

Methyl 2-ethoxy-2- / ^{: 1-} nitro-5- (2-chloro-4-trifluoromethyl-phenoxy) phenoxy-acetoacetate,

Methyl 2-n-butoxy-2 - / "2-nitro-5- (2-fluoro-4-trifluoromethyl-6-chlorophenoxy) -phenoxy / acetate,

Ethyl 1-methylthio - ^ - ^ - nitro-S- (2-cyano-4-trifluoromethylphenoxy) phenoxy / acetate,

n-butyl-2-phenylthio-2- / 2-nitro-5- (2-methyl-4-trifluoromethylphenoxy) phenoxy / acetate,

2-n-butylthio-2 ~ / 2-nitro-5- (2-nitro-4-trifluoromethyl) phenoxy_7-acetonitrile,

2-phenylthio-2- / 2-nitro-5- (2-bromo-4-trifluoromethylphenoxy) phenoxy-7-acetamide,

2-benzylthio-2- / 2-nitro-5- (2-fluoro-4-trifluoromethylphenoxy) phenoxy / ethanol,

2-phenoxy-2- / 2-nitro-5- (2,6-dichloro-4-trifluoromethylphenoxy) phenoxy / -1-chloroethane,

2-benzyloxy-2- / 2-nitro-5-2,4-bistrifluoromethylphenoxy) phenoxy-7-N-dimethylacetamide,

2-methoxy-2 - / "2-nitro-5 - '(2-chloro-4-trifluoromethylphenoxy) phenoxy / acetic acid,

Sodium 2-methoxy-2/2-nitro-5- (2-chloro-4-trifluoromethylphenoxy) phenoxy / acetate ,

Methyl 2-methoxy-2/2-nitro-5- (2-chloro-4-trifluoromethylphenoxy) phenoxy / acetate,

1-Methoxy-1/2-nitro-5 (2-chloro-4-trifluoromethyl) phenoxy-7-acetone, propargyl-2-methoxy-2/2-nitro-5 (2-chloro-4-trifluoromethylphenoxy) phenoxy / acetate.

β, β _/ β-trifluoroethyl-2-methoxy-2/2-nitro-5- (2-chloro-4-trifluoromethylphenoxy) phenoxy / acetate,

.beta.-methoxyethyl-2-methoxy-2 (2-nitro-5/2-chloro-4-trifluoromethylphenoxy) phenoxy / acetate,

β-hydroxyethyl-2-methoxy-2- / 2-nitro-5 (2-chloro-4-trifluorinated ethylphenoxy) phenoxy / acetate,

- 39 -

Methoxyethoxyethyl 2-methoxy-2- / 2-nitro-5 - (2-chloro-4-trifluoromethylphenoxy) phenoxy-7-acetate, β-chloroethyl-2-methoxy-2/2-nitro-5 (2-chloro-4-trifluoromethylphenoxy) phenoxy_7acetat,

Cyanomethyl-2-methoxy-2/2-nitro-5 (2-chloro-4-trifluoromethylphenoxy) phenoxy ^ acetate,

β-cyanoethyl-2-raethoxy-2/2-nitro-5 (2-chloro-4-trifluoromethylphenoxy) phenoxy_7acetate,

ß-nitroethyl-2-methoxy-2/2-nitro-5 (2-chloro-4-trifluoromethylphenoxy) phenoxy _> 7acetat and

ß-phenethyl-2-methoxy-2/2-nitro-5 (2-chloro-4-trifluoromethylphenoxy) phenoxy / acetate.

The compounds of the formula I can be prepared according to methods described in the literature for the preparation of analogous compounds and in particular according to the methods explained in the Examples.

Using the method described below, the diphenyl ether of Example 1 is tested for the control of the following weeds that grow between the crops listed below.

abbreviation conventional name -. scientific name weeds BYG barnyardgrass Echinochloa crusgalli buckwheat Fagopyrum esculentum CKL cocklebur Xanthium pensylvanicum DB Flaumtrespe Bromus tectorum EUP Vfolfsmilch Euphorbia heterophylla POX green foxtail Setaria viridis JOH Johnson grass Sorghum halepense MA marigold Tagetes spp. MG -. Morning Glory Ipaiüea spp. NUT yellow cypergrass Cyperus esculentus SMT smartweed Polygonum spp. TBW Fagopyrum tataricum

22 1980 -ze- scientific name abbreviation conventional name weeds Lycopersicon esculentum TCM tomato Avena fatua WHERE wild oats Abutilon theophrasti VEL velvetleaf crops Hordeum sativum BAR barley Zea mays CN Corn Gsssium hirsutum COT cotton Avena sativa OT oats Brassica napus RA rape Oryza sativa RI rice Beta vulgaris SB sugar beets Helianthus annua SF sunflowers Glycine max SOY soybeans Triticum aestivum WHT - wheat

The following test method is used. Seeds of selected crops and weeds are placed in soil in troughs. To run pre-emergence tests, the troughs are sprayed with the test compound immediately after seed introduction. To conduct Nachauflauftests allowed to germinate the seed. After growing in a greenhouse for 2 weeks, the growing plants are treated with the test compound. The compound to be tested is dissolved or dispersed in acetone or water and sprayed over the trays using a carrier volume corresponding to 467 l / ha in an amount in kg / ha, which is given in the following table. About 2 weeks after the application of the test compound, the growth state of the plants is observed and the phytotoxic effect of each compound is determined in the following manner: each species is scored on a scale of 0 to 100, where 0 indicates no activity and 100 represents total kill , The results

22 198 ©

for the monocotyledonous and dicotyledonous species are determined separately.

The diphenyl ether of Example 1 is primarily screened only against weeds and tested in a second study for weeds and eight major crops. The values of the first study are shown in Table II and the values of the second study in Table III.

The connection shows a pre-emergence activity. It also has an excellent post-emergence activity. Wheat, rice and corn are the most tolerant monocot crops, with soybeans having the most tolerable tolerance.

The first postemergence test shown in Table IV was conducted using four mature and hardened weed species, spike, marigold, tomato, and morning glory. The rice and wheat plants were younger and more susceptible than the weeds.

According to the test shown in Table V, the weeds consisted of buckwheat, milkweed, water pepper and Fagopyrum tataricum. The tested crops consisted of barley, oats, rice, soybeans and wheat.

2 2 19 8

Table II

First examination values% weed control

AM ¹ Vorauflaut postemergence at the' AD kg / ha 81 AD ^ 100 100 ' 2.24 48 96 100 100 0.56 8th 58 84 100 0.13 0

The weed species were as follows:

monocotyledons: BYG, DB, FOX, JON, NUT, WO dicots: CKL, MA, MG, TOM, VEL

1 average monocot

2 average dicots

22 1980

Table III

2. Examination in a greenhouse % Weed control or influence of crops

AM ¹ AD ² CN preemergence RA RI 0 SB postemergence 99 100 100 SF SOY WHT 'kg / ha 90 COT 100 0 100 100 97 100 100 30 20 40 2.24 44 58 80 25 80 0 100 100 80 100 100 5 0 0 1.12 25 28 25 0 90 99 50 0 0 0 0.56 22 26 10 0.28 85 75 50 2.24 90 100 50 70 35 1.12 86 100 30 60 25 0.56 '82 98 0.28

average monocot average dicotyledonous

Table IV '

Postemergence investigation on older plants % weed control or influence

der_ Nutzpflanzen __

By-

kg / ha VTHT RI CKL * MA TOM MG cut 0.28 60 80 90 80 85 100 89 0.13 50. 50 85 50 75 88 77 0.07 40 30 80 45 25 100 62 0.03 40 25 75 40 25 100 60 0.02 35 25 30 40 25 98 48 0.01 - 10 40 20 .20 • 95 4J4 63

The weed plants were 8 weeks old and rice and wheat were 2 weeks old.

22 19 80

- 34 Table V

Post-emergence test on hardened weeds to control dicotyledonous weeds % Influence on crops or weed control

weeds

kg / ha BW EUP SMT - 100 TBW BAR 0.56 100 78 0.28 95 95 95 100 68 0.13 90 96 90 100 80 P 07 80 83 96 100 70 0/03 68 45 100 ' AVE 83 80 100

crops

OT RI SPY WHT

90 55 85 40

88 40 78 40

75 33 65 30

60 5 58 35

The herbicidal activity of the diphenyl ethers of Examples 19-19 of the present invention is demonstrated by tests using the following representative species.

approximately number

barnyardgrass the seed Einkeimblätt Flaumtrespe (Echinochloa crusgallx) 25 engined Johnson grass (Bromus tectorum) 20 foxtail (Sorghum halepense) 25 yellow cypergrass (Setaria spp.) 25 wild oats (Cyperus esculentus) 5 (Avena fatua) 20 Zweikeimblätt- cocklebur engined marigold (Xanthium pensylvanicum) 3 Morning Glory (Tagetes spp) 15 tomato (Ipcrooea spp) 10 velvetleaf (Lycopersicon esculentum) 15 (Abutilon theophrasti) 15

The test method described above is used. The results are shown in Table VJ.

Table VI

Connection of example no.

1.

Second

Third

4th

5th

6th

7th

8th.

9

 10

 11

 12

 13

 14

 15

 16

 17

 18

 19th

Mangle 0.5 6 kg / ha

preemergence

AT THE

25

18-

38

43

51

12

22

58

• 28

40

18 47 37 0 40

AD

100

7 4

78 76 60 81 22 60 64 52 38 79 59

Postemergence. AM AD

92

83

88

88

82 ·

50

10

20 20 22 61

10 27 28

βχ

20

100

100

100

100

100

99

46

36

90

100

88

98

70 61 65 14 100 84 Quantity 2.24 kg / ha

preemergence

AT THE .

78 67 69 90 73 58

2 63

83 79

61 74 75

73 48

100

99

94

94 100

90

95

52

96

70 96 61 75 · 86 32

, 80 1.0 0

Postemergence AM .., AD

98 93 98 97 89 64 17 13 58

28 68

10 45 40 8 70

100

100

100

100

100

100

96 99 10 83 93 71 56 100 82

average monocots

average dicotyledonous

as

22 19 80 -a

Further, as specific compounds of the formula I, all compounds of the formula I should be mentioned, in which however (with reference to the symbols used in the formula I) the following changes occur:

(a) X in the individual ethers in question is by

substitutes another group or atom selected from H ₇ Br, Cl, F, J or CF ₃ ;

(b) Y is through in each of the ethers in question

substitutes another group or atom selected from H, Br, Cl, F, J or CF ₃ ;

(c) W is through in each of the ethers in question

substitutes another group or atom selected from O, S, SO or SO ₂ ;

(d) R is replaced by the individual ethers in question

by another group selected from nC.Hg, phenyl, 4-chlorophenyl, 3,4-dichlorophenyl, 4-fluorophenyl, 4-bromophenyl, 3-iodophenyl, 4-trifluoromethylphenyl, benzyl, CgH ₅ (CH ₂ J ₄ - and phenethyl;

(e) Q is different in the individual ethers in question

and is selected from (CH ₃ J ₀ , CH ₃ , (CH ₂ ) ₂ , (CH ₂ ) ₄ , CH = CH, CH ₂ CH = CH ₂ and CH ₂ Ch ₂ ;

(f) Z in the individual ethers in question is by

substitutes another group selected from CO ₃ H, CO ₂ / CONH ₂ , CN, CH ₂ OH, CH ₃ Cl and CH ₂ OCH ₃ ;

(g) Z goes through the individual ethers in question

substitutes another group selected from CO ₃ R, COSR ¹ CONHR ¹ , CON (R ¹ J ₀ , COR ¹ , CO ₀ (CR ² R ³ ) CO ₀ R and OR ¹ , where R is in the case of the last seven groups CH _3, nC ₄ H _9, CH ₂ CH = CH _2, CH ₂ CH ₂ CH = CHCH ₂ CH _3, CH ₃ CN, (CH ₃ J ₄ CN, C = CCH _3, C = CCH ₂ CH ₃ CH ₂ CH ₃ , CH ₂ CH ₂ Cl, CH ₂ CH ₂ Cl, CH ₂ CHBrCH ₃ , CH OH, (CH ₂ J ₃ CH CH ₂ CH ₂ CH ₃ , (CH ₂ J ₄ OCH ₃ , CH ₂ O (CH ₂ J ₄ OCH ₃ , 0 (CH ₂ J ₃ CH ₃ , CH ₂ CF ₃ , (CH ₂ ) ₂ NO ₂ , (CH ₂ ) ₄ NO ₂ , cyclopropyl, cyclooctyl, phenylmethyl or phenyl-n-butyl, then if Z is CO ₂ (CR ² R) _m ^c O ₂ ^R ^ ^O ^ ' ^the group - (CR ² R ³ ) _m ~ is made of CH ₃ , CH (CH ₃ ), C (CH ₃ J ₂ ,

19 80. S-

CH ₂ CH (CH ₃ ), CH (CH ₃ ) CH (CH ₃ ), (CH ₃ J ₃ , or (CH ₂ J ₂ C (CH ₃ J _{2) is} selected.

Specific examples of herbicidal compositions according to the invention are given below. In this case, the abbreviation "WS" means active ingredient, which is the diphenyl ether of Examples 1, 3, 4 or 5 or, depending on the solubility, etc., is a diphenyl ether of another of the above examples. It should be noted that the indicated agents, depending on the WS content, require dilution with further liquid (usually water) or an agriculturally acceptable solid diluent or carrier.

Ready-to-use solid preparations

dust

Weight percentage WS 0.1

Talk 99.9

Granules (average diameter o, 5 to 1.5 mm)

Weight percentage WS 0.1

Attalpulgitton 99.9 (0.4 to 0.8 mm)

Liquid preparations

_ Percent by weight

^WS 0.1

Acetone / water 99.9

emulsion

Wt .-% emulsifiable 0.1 concentrate containing 50 wt .-% WS ,. 5% by weight of calcium dodecylbenzenesulfonate, 5% by weight of octylphenoxypoly (ethyleneoxy) ethanol, containing on average 9 ethyleneoxygruppan, contains (borderline)

2 19

Liquid preparations (continued)

Weight percent water 99.9

suspension

- Wettable powder containing 0.1

'50% by weight VB, 21.5% by weight kaolin, 25.0% by weight precipitated silica, 3% by weight sodium adenylnaphthalenesulfonate. and sodium lauryl

- contains sulfate

Xanthan gum (long-chain 0.25

Polysaccharide obtained by fermentation of molasses)

Propylene glycol 5.0

Water 94.65

Solid concentrate .

Weight percent dust concentrate

WS 95.0

Talk '5.0

Liquid or semi-liquid water-soluble or water-dispersible concentrates

solution

weight

WS 1.0

Octylphenoxypoly-1,5

(Ethyleneoxy) ethanol, containing an average of 9 Äthylenoxygruppen

(surfactant)

198

weight Flowable liquid suspension

paste

WS 50.0

Octylphenoxypoly (ethyleneoxy) ethanol containing an average of 9 ethyleneoxy groups (surfactant)

Natriunpolyacrylat 0.5

Xanthan gum 0.05

Propylene glycol 5.0

Water 42.45

WS 5.0 Palm oil 28.0 propylene glycol 5.0 xylene 21.0 Octylphenoxy poly (ethyleneoxy) - 10.0 ethanol, containing by average 9 ethyleneoxygen groups calcium stearate 4.0

Claims (18)

2 2 19 8 invention claim 1. A herbicidal composition, characterized in that it comprises as active ingredient at least one compound of the formula given below WR O-CH NO ₂ ^ QZ in which. X is hydrogen, halogen, trifluoromethyl, (C ₁ -C ₄ ) - Alkyl, cyano or nitro, Y is hydrogen, halogen or trifluoromethyl, W is O or S (O), where ρ is 0 to 2, R is (C ₁ -C) -alkyl, phenyl, halogen-substituted phenyl, trifluoromethyl-substituted phenyl or phenyl- (C ₁ -C ₄ ) -alkyl,
Q (CHp), wherein η is 0 to 4, or (C ^ ^- Cg) - alkenylene means
Z is CO ₂ R ¹ , CO ₂ H, CO ₂ , CONH ₃ , CONHR ¹ , COSR ¹ , CON (R ¹ ) ₂ , CN, CH ₂ OH, CH ₂ Cl, COR ¹ , CH ₂ OCH ₃ , CO ₉ (CR ² R ³ ) CO ₉ R ¹ or OR ¹ stands, 2 2 19 8 0 - AO - in which R ^{1 is} (C ₁ -C ₄ ) -alkyl, (C ₃ -C ₆ ) -alkenyl, cyano- (C ₁ -C ₄ ) -alkyl, (C ₃ -C ₆ ) -alkynyl, (C ₃ -C ₄ ) -Haloalkyl, (C ₁ -C ₄ ) -hydroxyalkyl, (C ₁ -C ₄ ) -alkoxy- (C ₁ -C ₄ ) -alkyl, (C ₁ -C ₄ ) -alkoxy- (C ₁ -C ₄ ) -8KOXy- (C ₁ -C ₄ ) -alkyltrifluorinethyl, (C ₃ -C ₄ ) -nitroalkyl, (C ₃ -Cg) -cycloalkyl or phenyl (C ₁ -C) -alkyl, 2 3 R and R are the same or different and are selected from hydrogen and 24ethyl, m is 1 to 3, the 2 3 -CR R groups are the same or different when m ^ 1 and, when Z is CO ₃ H, an agriculturally acceptable salt containing a compound of formula I together with an agriculturally acceptable carrier diluent and optionally a surfactant , 2. Composition according to item 1, characterized in that the compound of formula I according to item 1 of the structure CF. corresponds to, where ^1VW 2 X is hydrogen, halogen, trifluoromethyl, (C ₁ -C ₄ ) alkyl, cyano or nitro, Y is hydrogen, halogen or trifluoromethyl, W represents O or SO, R (C ₁ -C ₄ ) -alkyl, phenyl or phenyl (C ₁ -C ₄ ) -alkyl is η 0 to 4,
ρ 0 to 2 means and 22 1980 Ha - 45 - Z is CO ₂ R, CH ₂ H, CO ₂ , CONH ₀ , CONHR ¹ , COSR, .1 C0N (R ') _{o /} CN, CH ₂ OH, CH ₂ Cl or COR ^1, V
where R stands for. or (C ₃ -C ₄ ) alkenyl 3. MitteJJL according to item 2, characterized in that WR is alkoxy, alkylthio, phenylthio, benzylthio, phenoxy or eenzyloxy and Z is carboxy or alkoxyearbonyl. 4. Composition according to one of the items 1 to 3, characterized in that Y stands for hydrogen and X is chlorine or cyano. 5. Composition according to one of the items 1 to 4, characterized in that R is (C, -C ₄ ) -alkyl, phenyl or phenyl (C ₁ -C ₄ ) -alkyl and Z is CO ₂ R ¹ , CO ₃ H, C0 ~, CONH _2, CONHR, CON (R ¹ J _2, CN, CH ₂ OH, CH ₂ Cl or COCH _3, wherein R ¹ is (C ₁ -C ₄ -alkyl-J. 6. A composition according to item 1, characterized in that the compound of formula I in item 1 has the following structure: in which 2 R is (C ₁ -C ₄₎ alkyl, m is ¹ 0 or 1 and n ¹ is 0 or 1. IV (CHJ _nl CO (CH,) CH-0 _ml 22 1980 7. Composition according to item 1, characterized in that X is Cl, Y is H, WR is OCH ₃ and QZ CO ₂ R ¹ , wherein R ^{1 is} (C ₁ -C ₄ ) alkyl. 8. Composition according to item 7, characterized in that R is methyl. 9. A composition according to item 1, characterized in that X is Cl, Y is H, WR is OCH ₃ and QZ CO ₂ R, wherein R ^{1 represents} (C ₃ -C ₆ ) alkenyl. 10. Composition according to item 9, characterized in that R stands for allyl. 11. A composition according to item 2, characterized in that Y is hydrogen and WR, X, (CH ₀ ) Z and (CH ₉ ) Z-SaIz correspond to the following meanings: 22 19 80 12. A composition according to item 2, characterized in that X is chlorine, Y is hydrogen, WR is OCH ^ and (CH ₀ ) Z is CO ₀ CH (CHO) -, or CO ₀ CH ₀ CH = CH ₀ . 13. A composition according to item 1, characterized in that X is chlorine, Y is hydrogen, W is 0 and (a) RC ₂ H ₅ is QZ is CO ₃ C ₂ H ₅ , (b) R is CH ₂ CgH ₅ and QZ is CO ₀ CH CH, (c) R is C ^ -H _n and QZ is CN £ 2 ° -> DO or (d) R is CH ₃ and QZ is CH ₂ OCH ₃ , (CH ₂ J ₂ CO ₂ CH ₃ , CO ₂ CH ₂ CO ₂ CH ₃ or CO ₂ CH (CH ₃ ) CO ₂ CH ₃ symbolized. 14. Composition according to one of the preceding points, characterized in that it contains 0.1 to 95% by weight of the active ingredient. 15. Composition according to one of the preceding points, characterized in that it in the form of (a) a dust or a   Granules or (b) is in the form of a formulation containing a surfactant which is a wettable powder, a concentrated liquid suspension, a solution, a water-dispersible paste, an emulsifiable concentrate or a flowable emulsion concentrate. 16. A method of controlling weeds, characterized in that on growing weeds or on the surface of a growth medium prior to the emergence of weeds, an agent according to any one of items 1 to 15 is applied in an amount sufficient to control the growth of the weeds , 17. The method according to item 16, characterized in that weeds are combated between agricultural crops. 18. The method according to item 17, characterized in that the agricultural crop consists of a cereal crop plant.