CS229683B2 - Herbicide agent and manufacturing process of effective component - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formulaI[Ar is a group shown by the formula II or formula III (Y is trifluoromethyl, halogen, nitro, cyano, or lower alkyl; b is 1-3); R<1> and R<2> H or lower alkyl; X is H, halogen, nitro, lower alkyl, or lower alkoxy; a and n are 1 or 2]. EXAMPLE:2-[40(40Trifluoromethylphenoxy)-phenoxy]-propionic acid-2-(4-chlorobenzyloxy)-ethyl ester. USE:A herbicide. Exhibiting improved herbicidal effect by its small amount. Having a resuscitation-inhibiting effect especially on perennial gramineous weeds. PROCESS:A compound shown by the formula IV (M is H or alkali metal) is reacted with a compound shown by the formula V (Z<2> is halogen) in a solvent such as hexane, ether, etc. at 0-100 deg.C, to give a compound shown by the formulaI.

Description

The present invention relates to a herbicidal composition comprising as active ingredient novel substituted phenoxypropionates. The invention further relates to a process for the preparation of these novel substituted phenoxypropionates and to their use as an active ingredient of herbicidal compositions.

In U.S. Pat. No. 4,046,553 (corresponding to JP-A 51-106 735) discloses that compounds of the formula R '' x ² ........

O- c h-c-z-h wherein

X ¹ and X ² are halogen,

Y is hydrogen or alkyl having 6 or fewer carbon atoms; and

Z is oxygen or sulfur, and their salts, esters, amides and halides have herbicidal activity.

In Japanese patent publication 52-131545 (corresponding to German patentnímu Pat. No. 2,617,804 states that the compounds of the formula · O- ^ ^o ^ ^o ^ ³ - _<0 ° - in which _R

R is hydrogen or halogen; and

Ri means

(a) a straight or branched (C 1 -C 12) alkyl group which is substituted by cyclohexyl, halophenyl, nitrophenyl, (C 1 -C 6) alkylphenyl, optionally mono- to trisubstituted phenoxy, and as substituents a halogen and / or an alkyl group having 1 to 4 carbon atoms; (C 5 -C 6) alkoxy, (C 1 -C 4) alkoxyalkoxy wherein the first alkoxy moiety contains 5 to 6 carbon atoms and the second alkoxy moiety contains 2 to 4 carbon atoms, the alkoxyethoxyethoxy group (1 to 4 carbon atoms in the alkoxy moiety) , a group of the general formula

bet

or at the 2-position or further away from the carboxyl group by a phenyl group, which may be - mono- or polysubstituted;

b) cyclohexenyl or C3-C4-phenylalkenyl in the alkenyl moiety;

(c) a (C 4-C alk) alkynyl group which is optionally mono- or disubstituted with a straight or branched (C až-C alky) alkyl group, a halogen, a phenyl group, a halophenyl group or a (C až-C alkyl) alkylphenyl group; alkyl, but R 1 is not unsubstituted propargyl or butynyl;

dj any of the following groups of formulas IV ‘, V‘, VI ‘, VII‘

CfaCH ₃ , O '

-R-CH-CH 2 ((°

-RfO-CO-N ^{7 and} %

-rt-o-co-Rs, / (v'l (νύ or

(e) C 1 -C 2 alkyl substituted by furyl, -tetrahydrofuryl, pyridyl or oxiranyl, having herbicidal activity, the symbols given in the formulas above have the following meanings:

R a is hydrogen, -C 1 -C 4 alkyl or C 1 -C 4 alkoxy,

R 5 represents hydrogen, C 1 -C 4 alkyl or phenyl, or

R a and R 3 together form a 4- or 5-membered, saturated or unsaturated -alkylene chain in which - the methylene group may be replaced by a group "O", "C", or

II

O-N-alkyl, wherein the alkyl contains 1 to 4 carbon atoms,

R 1 is hydrogen or C 1 -C 4 alkyl,

Z 'means an inorganic or organic anion,

R 1 represents a straight or branched alkylene group having 1 to 12 carbon atoms,

R 5 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, phenyl optionally substituted by halogen, nitro or / and C 1 -C 4 alkyl, or is of formula VIII 'or IX'

(IX ^f ) viirí

R 5 is C 1 -C 4 alkyl and in is 0, 1 or 2.

Japanese Patent Application 52-144,637 (corresponding to German Patent No. 2,623,558) discloses that the compounds of the general formula

O ~ CH-

in which

R may be the same or different from each other and is halogen, C1-C4alkyl or C1-C4alkoxy,

Y is oxygen or sulfur, n is 1 or 2, and

Ri means

(a) straight or branched (C 1 -C 12) alkyl substituted with cyclohexyl, halophenyl, nitrophenyl, (C 1 -C 4) alkylphenyl or formula (II), (III) or (IV) "

Г dl)

-O-CH 2 CH 2 N 4 (H 1) * 2 • -NR ₃ L.

(I V or is mono- or polysubstituted by the same or another group selected from the group consisting of hydroxy, halogen, thiocyanato and phenyl at position 2 or farther from Y;

b) a mono- or dialkylcyclohexyl group having 1 to 4 carbon atoms in the alkyl;

c] cyclohexenyl or C 3 -C 4 alkenyl optionally substituted by halogen, hydroxy, phenyl, halophenyl or C 1 -C 4 alkylphenyl;

dj a naphthyl or phenyl group, which in some cases is mono- or polysubstituted by C1-C4alkyl, C1-C3haloalkyl, trifluoromethyl, nitro, cyano, -SCN, -CHO, alkoxy C 1 -C 3 alkyl, C 1 -C 3 alkoxycarbonyl, aminocarbonyl, C 1 -C 4 dialkylamino or C 1 -C 2 alkylthio and may also contain halogen; or, when Y is O, R1 is also a straight or branched alkynyl group having 3 to 6 carbon atoms, which in some cases is mono- or polysubstituted by an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 6 carbon atoms; 4 carbon atoms, halogen, phenyl, halophenyl, or C1-C4alkylphenyl;

fj is a halo-cyclohexyl group optionally substituted by a C1-C4 alkyl group;

gj a group of formulas V ', VI', VII ', VIII', IX ', X', XI ', XII'

CH ₃ <v> -R-CH-CH., 11 VII -R 1'-O-CO-Re, (VII ") -R 1'-O-C0-0-R7,

ÍVIII ")

R7 / —Ri — O — CO — N \

R8 (IX ') —Ri' — CO — R9, (X “) —Ri' — O — SO2 — R7 (XI”) or —Ri' — S (O) _p —R7 (XII “)

h) C 1 -C 2 alkyl substituted by furyl, tetrahydrofuryl, pyridyl or oxiranyl;

i) a C 2 -C 4 alkyl group substituted with 3 to 7 chlorine atoms or fluorine atoms; or, if Y is sulfur, R 1 is

(k) a (C až-Ceny mají) alkenyl group having herbicidal activity, in the above formulas the general symbols have the following meanings:

R 2 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, hydroxyethyl or chloroethyl and

R '3 is hydrogen, (C 1 -C 4) alkyl, chloroethyl, phenyl, halophenyl, (C 1 -C 4) alkylphenyl, hydroxyethyl or (C 1 -C 4) aliphatic acyl, or

R a and R 5 together represent a 2-, 4- or 5-membered, saturated or unsaturated hydrocarbon R 7 represents an alkyl group having 1 to 4 di-chains in which the carbon atom may be replaced by -O-, -CO-, -NN, -NH - or - —N — alkyl, wherein the alkyl contains 1 to 4 carbon atoms,

R < 1 &gt; is hydrogen or (C1-C4) -alkyl,

Z 'means an anion of an inorganic or organic acid,

R 1 represents a straight or branched alkylene radical having 1 to 12 carbon atoms,

R 5 represents an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, an alkoxyalkoxy group having 3 to 12 carbon atoms, a hydroxyethyl group or a phenyl group which is optionally mono- or disubstituted halogen or a (C 1 -C 3) alkyl group,

R 6 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, phenyl optionally substituted by halogen, nitro or / and C 1 -C 4 alkyl, or-

a carbon atom, a phenyl group, a halophenyl group, a nitrophenyl group or an alkylphenyl group having 1 to 4 carbon atoms in the alkyl,

R e is hydrogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy,

R 9 is C 1 -C 4 alkyl and p is 0, 1 or 1; 2.

Furthermore, German patent no.

No. 812,571 (corresponding to Japanese Published Application 54-119,476) discloses compounds of the general formula

223683

IQ in which

X is fluorine or chlorine,

Y is hydrogen or chlorine,

R is hydrogen, methyl or ethyl; n is 0 or 2; and

Z ¹ is hydroxy, C 1 -C 6 alkoxy in which the alkyl moiety is optionally substituted with one to three halogen atoms, furthermore C 1 -C 4 alkoxyalkoxy in both alkoxy moieties, C 2 -C 4 alkenyloxy, alkynyloxy C 2 -C 4 cycloalkyl, C 3 -C 6 cycloalkyl of which the cycloalkyl moiety is optionally substituted with C 1 -C 4 alkyl, furthermore C 1 -C 4 alkoxycarbonylalkoxy, phenoxy wherein the phenyl moiety is optionally substituted with 1 to 3 halogens or (C 1 -C 4) alkyl, benzyloxy, glycidyloxy, (C 1 -C 4) alkylthio, (C 2 -C 4) alkenylthio, phenylthio, the phenyl of which is optionally substituted with 1 to 3 halogen atoms or alkyl groups with 1-4C, furthermore amino, C1-C4 alkylamino, C1-C4alkoxycarbonylmethylamino, hydroxycarbonylmethylamino, anilino, the phenyl of which is optionally substituted by 1 to 3 halogen atoms, pyridin-2-ylamino , -O-cation or halogen have herbicidal activity.

It has now been found that the novel substituted phenoxypropionates of the general formula (I)

tlj in which

R 1 and R ² are independently hydrogen or alkyl having 1 to 6 carbon atoms,

X represents a hydrogen atom or a halogen atom or a nitro group, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and n is each independently 1 or 2, and

Ar is a group of formulas Ia or Ib of said and defined formula I.

According to the invention, the novel compounds of the formula (I) are produced by converting them to a compound of the formula (II)

LIMB

(la) (Ibi where

Y is trifluoromethyl, halogen or nitro, cyano or (C1-C6) alkyl, and b is 1, 2 or 3, have herbicidal properties and can therefore be used as active ingredients of the herbicidal compositions.

Accordingly, the present invention provides a herbicidal composition which comprises as active ingredient at least one substituted phenoxypropionate in which:

Ar is as defined above and

M represents a hydrogen atom or an alkali metal atom, acting with a compound of formula III

С ^Нъ ° Ϋ f

7-CH-C-O-CH (CH 2 O-CH

(Ш)

in which

R ¹ , R 2, X, a and n have the above-mentioned meanings and

Z ¹ represents a halogen atom, optionally in the presence of an acid-binding agent and optionally in the presence of a diluent at a temperature between 0 ° C and 100 ° C.

Surprisingly, the substituted phenoxypropionates of the present invention, which have not been previously described in the literature, can be readily synthesized in high yields and are novel active compounds having excellent selective herbicidal activity against grass weeds without having any remarkable phytotoxicity against agricultural crop plants. It is particularly surprising that these compounds of the present invention possess excellent properties which the structurally similar compounds of the prior art do not possess, in particular that they exhibit sufficient herbicidal activity even in small quantities, yet are well tolerated by the plants and, moreover, perfectly it also counteracts the regeneration of weeds, in particular perennial monocotyledonous weeds, since they have an excellent long-lasting effect.

Preferred compounds produced in accordance with the present invention and accordingly the corresponding starting materials are those in which:

Ar represents a group of formula Ia or Ib, wherein

Y represents trifluoromethyl, fluorine, chlorine, bromine or iodine or nitro, cyano, methyl, ethyl, propyl, isopropyl, η-, iso-, sec or tert-butyl;

b is 1, 2 or 3;

R1 and R2 are each independently hydrogen or methyl, ethyl, n-propyl, isopropyl, η-, isc-, sec or tert-butyl;

X is hydrogen, fluorine, chlorine, bromine or iodine, nitro, methyl, methoxy, ethyl, ethoxy, n-propyl, n-propoxy, isopropyl, isopropoxy or η-, iso-, sec or tert, butyl or -butoxy and a and n are each independently 1 or 2.

If 4- (4-trifluoromethylphenoxy) phenol and 2-benzyloxyethyl-2-bromopropionate are used as starting materials in the process of the present invention, the reaction scheme can be illustrated by the following reaction scheme:

Examples of compounds of formula (II) which are used as starting materials for the process of the invention include the following compounds:

4- (4-Trifluoromethylphenoxy) phenol

4- (2-trifluoromethylphenoxy) phenol

4- (4-fluorophenoxy) phenol,

4- (2,4-dichlorophenoxy) phenol,

4- [phenoxy) phenol, l- (2-t-trifloormetУyl chlorfeooxy Jfenol ⁴ - ^(t -TR ^IFL oorme ^thyA -L ² -c ^hl or ^{phenoxy JF enol}

4- (3,5-dichloro-2-pyridyloxy) phenol,

4- (5-nitro-2-pyridyloxy) phenol,

4- (4-nitrophenoxy) phenol

4- (t-bromo-2-chlorophenoxy) phenol, 1- (t-trifluoromethyl-2-nitrophenoxy) phenol,

4- (2,6-tetrahydro-4-trifluoromethylphenoxy) phenol,

4- (2-cyain-4-trifluoromethylphenoxy) phenol,

4- (enoxy) phenol

4- (3-chloro-5-nitro-2-pyridyloxy) phenol,

4- (5-Trifluoromethyl-2-pyridyloxy) phenol, 1- (3-chloro-5-fluoromethyl-2-pyridyloxy) phenol,

4- (5-bromo-3-chloro-2-fluoridyloxy) phenol a

4- (t-chloro-2-methyleneoxyphenol) as well as their alkali metal salts, for example lithium, sodium and potassium salts.

· As examples of other starting materials, i.e. compounds of formula III, which, after ^one used in the process of the invention include the following compounds:

2-Benzyloxyethyl-2-chloro (or -bromo) propionate

3-Benzyloxypropyl 2-chloro (or -bromo) propionate

1-methyl-2-benzyloxyethyl-2-chloro (or

-bromo) propionate,

2ra-Methylbenzyloxyethyl-2-chloro (or

-bromo) propionate,

2- (2-fluorobenzyloxy) ethyl-2-chloro (or

-bromo) propionate,

2- (4-fluorobenzyloxy) ethyl-2-chloro (or

-bromo) propionate,

2- (2-chlorobenzyloxy) ethyl-2-chloro (or

-bromo-propionate,

2- (4-chlorobenzyloxy) ethyl-2-chloro (or

-bromjpropicnát,

2- (2,4-dichlorobenzyloxy) ethyl-2-chloro (or

-bromo-propionate,

2- (3,4-dichlorobenzyloxy) ethyl-2-chloro (or b

-bromo] propionate,

2- (З ^ -О-сЫогЬоппу ^ хуО e lhol-2-chloro (nzbb)

-bromipropionate,

2- (2-methylbenzyloxyethyl) -2-2-chloro (nzbo

-bromo-propionate,

2- (3 - ^^ 0001 ^ 100x16 thyl-2-chloro-r) (ппЬо

-bromlpropionate, 2- (4-methylbenzzolxy) olyl-C-2hlozeorbo

-bromlpropionate,

2- (4-benzylbenzyl) ethyl-2-chloro (para

-Oromlpropionate ^,

1-Methyl-2-α-methylOenzyloxyethyl-2-chloro (neo-O-rm) propioate,

2- (4-2-chloro-benzyloxy) -ethyl-2-chloro (or

-bromo-propionate,

2- [221’001301 ^ 100x10 thol-2-chloro (nzbo)

-brOmjpropionát,

2- (4-fluorobenzyloxy) ethyl-2-chloro (or

-OrrmJpropioeate,

1-Methyl-2- (2-fluorobenzyloxy) ethyl-2-

-chlor (ebbr -bromJprrpireate,

3- (2-fluorobenzyloxy) propyl-2-chloro (or

-bromo) propionate,

2- (2-nitro-azyloxy) -ethyl-2-carboxylic acid (or 2- (2-nitro-azyloxy) -ethyl-2-carboxylic acid;

-bromo] propionate,

2- (4-0-4000 ^ x100x1 thyl-2-chloro)

-brOmjpropiOnát,

2- (4-methylbenzyloxy) ethyl-2-chloro (para

-bromJprr · pirnate,

2- (2-Methoxybenzyloxy) ethyl-2-20-chloro (or

-bromo-propionate,

3- (d-fluorobenzyloxy) propyl 2-chloro (or bromopropioate).

The process of the present invention is preferably carried out in the presence of a diluent. All inert solvents can be used for this purpose.

Examples of such solvents or diluents are water, aliphatic, alicyclic and aromatic hydrocarbons, which may in each case optionally be chlorinated (such as hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, methylbechloride, chloroform, tetracloggmbethane, btholeecloroC, trichlorethylene). Ethers (such as diethyl ethyl, methoxietol ether, diisopropol ether, carbon monoxide, propylene oxide, dioxane and tetrofodofuran); ketones (such as acetone, methacrylic acid, methylthiocarbonyl and methylisopropyl ether) nitriles (such as acetonitrile, propionitrile and acrylozitrile); alcohols (such as methanol, ethanol, isopropaeol, butanol, and ethylene glycol); esters (such as tert-butyl acetate and amyl acetate); acid amides (such as dimethylformamide and Cimethylacetamide C); sulfoey and sulfoxides ( such as dimetholsulfoxide and sulfolae] and bases (such as poridia).

The process of the invention is preferably carried out in the presence of an acid binding agent. Examples of such acid binding agents include alkali metal hydroxides, carbonates, carbonates and alkoxides, and targets, amines such as trietholamine, diethylanilium, and pyridine.

The process according to the invention can be carried out over a wide temperature range. In general, the reaction is carried out at temperatures between -20 ° C and the boiling point of the reaction mixture, preferably at temperatures between 0 ° C and 100 cc.

The process according to the invention can be carried out at atmospheric pressure, although it is also possible to work at elevated or reduced pressure.

The compounds of the formula III which are used as starting materials for the process according to the invention have not been described in the literature.

Compounds of formula (III) are prepared by treating a compound of formula (VIII)

CH4 O

Z 1 —CH — C — Z ¹ (VIII) wherein each of Z ¹ independently and independently of one another is halogen, acts by a compound of formula IX h (CH ₂ h ^OCH)

(IX) wherein

R ¹ , R ² , X, a and ⁿ are as defined above.

Examples of compounds of formula VIII which are used as starting materials in the preparation of compounds of formula III include:

2-bromopropionyl bromide and 2-chloropropionyl chloride.

Examples of other starting materials of formula (IX) used in the preparation of compounds of formula (III) include:

2-Benzoloxyethainol

3- beezoloxyprΌpaeol,

1-Methanol-2-Oenzyloxoethanol

2- (2-chlorobenzyloxy) ethanol, 2- (2-chlorobenzyloxy) ethanol,

2- (4-chlorobenzyloxy) ethanol,

2- (d-chlorobenzyloxo) ethanol,

2- (2,4-chlorobenzoloxy) ethanol.

2- (2,6-dichlorobenzyloxy) ethanol,

2- (3,4-dichlorobenzyloxy) ethanol,

2- (2-methylbenzyloxy) ethanol,

2- (4-methylbenzyloxy) ethanol,

2- (2-methoxybenzyloxy) ethanol,

2- (4-methoxybenzyloxy) ethanol,

2- (2-bromobenzyloxy) ethanol,

2- (4-bromobenzyloxy) ethanol,

1-Methyl-2-α-methylbenzyloxyethanol

2- (2-fluorobenzyloxy) ethanol,

2- (3-fluorobenzyloxy) ethanol,

2- (4-fluorobenzyloxy) ethanol,

2- (2-nitrobenzyloxy) ethanol,

2- (3-nitrobenzyloxy) ethanol

2- (4-nitro-benzyloxy) ethanol,

1-Methyl-2- (2-fluorobenzyloxy) ethanol

3- (2-fluorobenzyloxy) propanol,

3- (4-fluorobenzyloxx) propanol.

If 2-bromopropiosyl bromide and 2-benzylxxyethalol are used as starting materials, the reaction scheme can be illustrated as follows:

CHj o

Br-CH-C-Br + 4 OCH _Z CH _Z ^O C ^H ^^>

CH ₃ O—

----> Вг-СН-С0-СИ., СИ _г 0СН ₂ - <^ ⁺ HI2r

In the preparation of the compounds of formula III, one of the solvents or diluents described above for the process according to the invention is preferably used in order to obtain the final products in high purity and in high yield. This reaction is also preferably carried out in the presence of an acid binding agent as described above for the process of the invention.

The reaction conditions, i.e. temperature and pressure, are also selected from those mentioned above for the process of the invention.

The active compounds of the formula I according to the invention show an excellent selective herbicidal action when used as a weed control agent in the case of intensive or pertinent application.

Since the active compounds of the present invention have only a low toxicity to warm-blooded animals or are not toxic to warm-blooded animals at all, and because they exhibit good selectivity towards agricultural crop plants, i. They are not phytotoxic to agricultural crops, they can be advantageously used as herbicides for controlling weeds.

The active compounds according to the invention influence the growth of the plants and can therefore be used as defoliants, desiccants, dicotyledons, germinating agents and, in particular, as weed control agents. 'Weeds', in the broadest sense, are those which grow in places where their growth is not desired.

Whether the compounds according to the invention act as total or selective herbicides depends in particular on the amount applied.

The active compounds according to the invention can be used, for example, for controlling the following plants:

dicotyledonous weeds of the genera mustard (Sina ^ s), watercress [Adhesives], bedstraw (Galium), chickweed (Stellaria) chamomile (Matricaria), chickweed (Anthemis), quail (Galmsoga), goosefoot (Chenopodium), nettle (Urica) ragwort (Senecm), amaranth (Amaranthus), purslane (Portulaca), beetroot (Xanthium), bindweed (Convolvulus), barley (Ipompnα), moss (Polygonum), gathering (Sesbania), ambrosia (Ambrosia), thistle (Cirsium) Thistle (Carduus), · Milk (Smchus), Mustard (Rorippa), Rotala, Lindernia, Dead-nettle (Lamium), Speedwell (Veorιzica), Abutilon (Abutilon), Emex, Durman (Datura), Violet (Viola), Hemp (Galeopsis) ), poppy (Papaver), cornflower (Centaurea) and eggplant (Solanum); and monocotyledonous weeds of the species Echinochloa, shear (Setaria), millet (Panicum), dewberry (Digitaria), timothy (Phleum), meadowgrass (Poa), fescue (Festuca), eMne (Eleusine), Brachiaria, ryegrass (Lolium) ), brome (Bromus), oats (Avena), plum (Cyperus), sorghum (Sorghum), wheatgrass (Ag ^ rm), hawk (Cynodon), Monooharia, Fimbristylis, arrowhead (Sagittaria), Eleocharis, Scirpus, Paspalum , Ischaemum, Splienoclea, Dactyloctenium, distemper (Agrostis), foxtail (A ^ i ^] ^ <^ (^ i ^ rus), chuindelka (Apera).

The active compounds of the present invention can be used as selective herbicides in, for example, the following crop plants:

dicotyledonous plants of genera:

cotton (Gossypium), soybean (Glycine), beet (Beta), carrot (Daucus), bean (Pkaseo229683 lus), peas (Pisum), potato (Solanum), flax (Linen), bean (Ipomoea), bob (Vida) , tobacco (Nicotiana), tomato (Lycopersicon), peanut (Arachis), kale (Brassica), lettuce (Lactuca), cucurbit (Cucumis and Cucurbita);

monocotyledonous plants of genera:

rice (Oryza), maize (Zea), wheat (Triticum), barley (Hordeum), oats (Avena), rye (Secale), sorghum (Sorghum), millet (Panicum), sugarcane (Saccharum), pineapple (Ananas) ), asparagus (Asparagus) and onion (Allium).

However, the use of the active compounds according to the invention is by no means limited to these genera but also includes other plants in the same way.

Depending on the concentrations, the compounds can be used for the total control of weeds, for example in industrial areas and on railway tracks, as well as on roads and places with possible tree growth.

They can also be used to control weeds in permanent crops such as wooded areas, ornamental tree crops, orchards, vineyards, citrus plantations, butternut crops, banana plantations, coffee plantations, tea plantations, on rubber, coconut, cocoa, berry and hop plantations as well as selective weed control in annual crops.

In particular, the active compounds according to the invention can be used for controlling the following plants:

hedgehog (Echinochloa crus-galli), European dew (Digitaria adscendens), eleusine (EÍeusine indica), green grass (Setaria viridis), deaf oats (Avena fatua), foxtail (Alopecurus aequalis), shear (Setaria lutescens), creeping grass (Agropyron repens) or wheatgrass (Agropyron tsukushiense).

In addition, these compounds exhibit excellent herbicidal activity as well as the ability to inhibit further growth, for example in the case of Sorghum halepense or Cynodon dactylon.

The active substances can be converted into the customary formulations such as solutions, emulsions, wettable powders, suspensions, dusts, soluble powders, granules, suspension or emulsion concentrates, natural and synthetic materials impregnated with the active substance and very fine capsules in polymeric substances.

These preparations can be prepared in a known manner, for example by mixing the active compounds with fillers, i.e. liquid or solid diluents or carriers, optionally using surface-active agents, i.e. emulsifiers and / or dispersants and / or foaming agents. When water is used as a carrier, for example, organic solvents can also be used as co-solvents.

Especially as solvents, especially aromatic hydrocarbons such as xylene, toluene or alkyl naphthalenes, chlorinated aromatic hydrocarbons or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic or alicyclic hydrocarbons such as cyclohexane or paraffinic hydrocarbons may be used as liquid diluents or carriers. , for example, mineral oil fractions, alcohols such as butanol or glycol, and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strongly polar solvents such as dimethylformamide or dimethylsulfoxide, and water.

Solid carriers can be natural minerals such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomite, and ground synthetic minerals such as highly dispersed silicic acid, alumina and silicates. Crushed and fractionated natural materials, such as limestone, marble, pumice, sepiolite and dolomite, as well as synthetic granular materials of inorganic or organic flours and granules of organic material, can be used as solid carriers for the granules. such as sawdust, coconut husks, corn sticks and tobacco stems.

Non-ionic or anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates and arylsulfonates, as well as albumin hydrolysis products can be used as emulsifiers and / or foaming agents. Dispersing agents include, for example, waste sulphite lyes and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latex products such as gum arabic, polyvinyl alcohol and polyvinyl acetate may also be used in the compositions.

It is also possible to use dyes such as inorganic pigments such as iron oxide, titanium dioxide and ferrocyanide blue, and organic dyes such as alizarin dyes, azo dyes and metallic phthalocyanine dyes, and trace elements such as iron, manganese, boron, copper, cobalt, molybdenum and zinc.

These preparations contain 0.001 to 100% by weight of active ingredient, preferably 0.005 to 95% by weight of active ingredient.

The active compounds according to the invention may be used as such or in the form of weed control agents also in admixture with known herbicides, with the use of ready-to-use preparations or formulations prepared immediately before use in a storage tank. Mixtures with other known compounds are also useful, such as fungicides, insecticides, acaricides, nematicides, antifungal agents, growth regulators, plant nutrients, as well as soil improvers.

The active compounds may be administered as such, in the form of concentrates or dosage forms which are prepared by further dilution of the concentrates, for example in the form of ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They can be used in conventional manner, for example by watering, spraying, spraying, sprinkling or dusting.

The amount of active compound in the ready-to-use preparations can vary within wide limits depending on the conditions. In general, it is from 0.01 to 95% by weight of active compound, preferably from 0.05 to 60% by weight of active compound.

The compounds according to the invention can also be applied by the so-called ultra low volume (ULV) method, in which the formulations used can contain up to 100% of the active ingredient.

The active compounds can be applied after the emergence of the plants or before the emergence of the plants, i.e. post-emergence or pre-emergence. They can also be worked into the soil before sowing.

The amount of active ingredient used may vary within wide limits. This amount depends essentially on the type of effect desired. In general, the application rate is between 0.01 and 2 kg / ha, preferably between 0.05 and 1 kg / ha.

The present invention encompasses a herbicidal composition comprising, as an active ingredient, at least one compound of the formula I in admixture with a solid diluent or carrier or in admixture with a liquid diluent or carrier containing a surfactant.

The present invention also encompasses a method for controlling weeds, comprising at least one compound of the formula I alone or in the form of a preparation containing at least one as active ingredient. the compound of formula (I), in admixture with a diluent or carrier, is applied to the weeds or areas where the weeds occur.

The present invention also relates to a method of protecting crops from weed damage, comprising applying to the areas in which the crops are grown immediately before and / or during the cultivation period at least one compound of the formula I alone. or in admixture with a diluent or carrier.

Obviously, the conventional crop harvesting methods can be improved by the present invention.

The preparation and composition of the compositions of the present invention are illustrated by the following examples. The compounds of the formula I according to the invention are designated in these examples by a number (in parentheses) corresponding to the numbering of the examples which illustrate the preparation of the active compounds. The term "parts" refers to parts by weight.

Example 1 parts of compound (1), 80 parts of a 1: 5 mixture of diatomaceous earth powder and clay, 2 parts of sodium alkylbenzene sulfonate and 3 parts of sodium alkylnaphthalene sulfonate-formaldehyde condensation product are converted to a powder and thoroughly homogenized to obtain a wettable powder. This wettable powder is diluted with water before use.

Example 1 parts of compound [11], 55 parts of xylene, 8 parts of polyoxyethylene-alkylphenyl ether and 7 parts of alkylbenzenesulfonic acid calcium salt are mixed with each other with stirring to obtain an emulsifiable concentrate. The emulsifiable concentrate is diluted with water before use.

Example 1 and parts of compound (12) and 98 parts of powdered clay are mixed homogeneously to a powder which is used as a dusting powder.

He said ad i v

1.5 parts of compound (13), 0.5 parts of isopropyl hydrogen phosphate and 98 parts of powdered clay are sprayed and mixed to give a dust.

Example v

Add 25 parts of water to a mixture of 10 parts of compound (14), 30 parts of bentonite (montmorillonite), 58 parts of talc and 2 parts of ligninsulfonic acid salt, and mix well. The resulting mixture is extruded into a 10 to 40 mesh particle size granulate and then dried at 40 to 50 ° C to give a granulate.

Example in i

By means of a rotary mixer, 95 parts of mineral clay are dispersed into 0.2 to 2 mm particles, and then a solution of 5 parts of compound (2) in an organic solvent is uniformly sprayed onto the surface of the particles while the stirrer is rotating. The particles are then dried at 40-50 ^° C to give a granulate.

The herbicidal activity of the compounds of the formula I is illustrated by the following biological tests, in which the compounds of the formula I according to the invention are indicated (in parentheses) with a number which corresponds to a corresponding example illustrating a process for the preparation of active compounds.

Compounds of the following formulas were used as known comparative compounds:

These compounds are disclosed in Japanese Published Patent Application 51-106 735.

CH 2 O

O-CH-s-O-CH μ _of O

This compound is disclosed in Japanese Published Patent Application 52-131,545.

c = l) =

CH ₃ P

O-C H- c-o-C

This compound is disclosed in Japanese Published Patent Application 52-144 637.

(d -) = re

This compound is disclosed in Japanese Patent Application 54-119,476.

Example A

To test the effect of pre-emergence application to weeds and crops in the above fields:

Production of active substance:

carrier: 5 parts by weight of acetone emulsifier: 1 part by weight of benzyloxypolyglycol ether

The active preparation in the form of an emulsifiable concentrate is obtained by mixing 1 part of the active ingredient with the indicated amount of carrier and emulsifier. The required amount of preparation is obtained by dilution with water.

Test performance:

Peanut (Arachis), Pea (Pisum), Cotton (Gossypium) and Soybean (Glycine) seeds are planted in pots (1000 cm ² ) in a greenhouse. The seeds are covered with a layer of soil 1 cm high in which seed of Agropyron repens, Echinochloa crus-galli and Setaria lutescens were mixed. One day. after sowing, 10 ml of the above-prepared solutions containing 500 ppm, 200 ppm, 100 ppm and 50 ppm of active substance are uniformly applied to the soil surface.

weeks after. The herbicidal effect and the degree of phytotoxicity are evaluated using a cd scale of 0 to 10 according to the following scale.

The herbicidal effect is evaluated as compared to untreated control plants as follows:

evaluation of the degree of weed damage (based on untreated control plants)

100 ° / o. (dried plants) at least 90% but less than 100% at least 80% but less than 90%

Ί at least 70 ° / o but less than 80 ·% at least 60 ° / o but less than 70% at least 50 ° / o but less than 60% at least 40% but less than 50% at least 30% but less less than 40% at least 20% but less than 30% at least 10% but less than 20% less than 10% (ineffective)

Phytotoxicity to useful plants is evaluated as compared to untreated control plants as follows:

evaluation degree of phytotoxicity (based on untreated control plants) at least 90% (extinction) at least 80% but less than 90% at least 70% but less than 80% and less than 60% but less than 70% а ^ рсй 50 % · But less than 60% at least 40% but less than 50% 30 ^o / o but less than 40% but less than 20%, but less than 30% and at least 10% but less than 20% more 0 0% but less than 10% 0% (the active substance is not phytotoxic)

The results of the tests are summarized in Table 1 below, in which the symbols in v g denote the following weeds v useful crops: v: rye (Agropyron repens), b: hedgehog (Echinochlov crus-galli) c: leg (Setaria lutescens) d : peanuts (Arachis) e: peas (Pisum) f: cotton (Gossypium) g: soya (Glycine).

compound number amount of active substance kg / ha TABLE 1 herbicidal effect of weeds v b c d phytotoxicity of the useful plant e f g 1 0.5 10 10 10 0 0 0 0 0.2 10 10 10 0 0 - 0 0 0.1 8 9 10 0 0 0 0 0.05 6 7 9 0 0 0 0 3 0.5 10 10 10 0 0 0 0 0.2 10 10 10 0 0 0 0 0.1 8 9 10 0 0 0 0 0.05 6 7 9 0 0 0 0 4 0.5 10 10 10 0 0 0 0 0.2 10 10 10 0 0 0 0 0.1 8 9 9 0 0 0 0 0.05 6 7 8 0 0 0 0 36 0.5 10 10 10 0 0 0 0 0.2 10 9 10 0 0 0 0 0.1 8 8 9 0 0 0 0 0.05 6 7 8 0 0 0 0 37 0.5 10 10 10 0 0 0 0 0.2 10 10 10 0 0 0 0 0.1 8 9 10 0 0 0 0 0.05 7 8 9 0 0 0 0

compound number amount of active substance kg / ha herbicidal effect of weeds a b c d phytotoxicity of the useful plant e f g 38 0.5 10 10 10 0 0 0 0 0.2 10 10 10 0 0 0 0 0.1 8 9 10 0 0 0 0 0.05 7 8 10 0 0 0 0 39 0.5 10 10 10 0 0 0 0 0.2 10 10 10 0 0 0 0 0.1 9 9 10 0 0 0 0 0.05 8 8 9 0 0 0 0 29 0.5 10 10 10 0 0 0 0 0.2 10 10 10 0 0 0 0 0.1 10 10 10 0 0 0 0 0.05 9 10 10 0 0 0 0 44 0.5 10 10 10 0 0 0 0 0.2 10 10 10 0 0 0 0 0.1 9 9 10 0 0 0 0 0.05 8 7 9 0 0 0 0 14 0.5 10 10 10 0 0 0 0 0.2 10 10 10 0 0 0 0 0.1 8 8 9 0 0 0 0 0.05 6 6 8 0 0 0 0 58 0.5 10 10 10 0 0 0 0 0.2 10 10 10 0 0 0 0 0.1 8 8 9 0 0 0 0 0.05 6 6 8 0 0 0 0 63 0.5 10 10 10 0 0 0 0 0.2 10 10 10 0 0 0 0 0.1 10 10 10 0 0 0 0 0.05 9 9 9 0 0 0 0 64 0.5 10 10 10 0 0 0 0 0.2 10 10 10 0 0 0 0 0.1 9 9 9 0 0 0 0 0.05 8 8 9 0 0 0 0 65 0.5 10 10 10 0 0 0 0 0.2 10 10 10 0 0 0 0 0.1 9 9 9 0 0 0 0 0.05 8 9 9 0 0 0 0 20 May 0.5 10 10 10 0 0 0 0 0.2 10 10 10 0 0 0 0 0.1 9 9 9 0 0 0 0 0.05 8 8 9 0 0 0 0 22nd 0.5 10 10 10 0 0 0 0 0.2 10 10 10 0 0 0 0 0.1 9 9 9 0 0 0 0 0.05 8 8 9 0 0 0 0 24 0.5 10 10 10 0 0 0 0 0.2 10 10 10 0 0 0 0 0.1 9 9 9 0 0 0 0 0.05 8 8 8 0 0 0 0 72 0.5 10 10 10 0 0 0 0 0.2 9 10 9 0 0 0 0 0.1 8 9 9 0 0 0 0 0.05 7 8 8 0 0 0 0 74 0.5 10 10 10 0 0 0 0 0.2 10 10 10 0 0 0 0 0.1 9 9 9 0 0 0 0 0.05 8 9 9 0 0 0 0 comparative 0.5 7 9 9 0 0 0 0 merge- 0.2 5 7 8 0 0 0 0 nina A-1 0.1 2 5 6 0 0 0 0 0.05 0 2 4 0 0 0 0 comparative 0.5 9 10 10 0 0 0 0 merge- 0.2 7 8 8 0 0 0 0 nina B-1 0.1 3 6 7 0 0 0 0 0.05 0 3 4 0 0 0 0

Example Β

Test for herbicidal activity against weeds and useful plants when applied to the leaves of plants in higher fields

Seeds of soybean (Glycine), radish (Raphanus) and beet (Beta) are sown in soil filled in pots (2000 cm ² ); the seeds are then covered with a 1 cm high layer of soil in which the seeds of the hedgehog (Echinochloa crus-galli), the dew (Digitaria adsendens), eleusine (Eleusine indica), green scar (Setaria viridis), deaf oat (Avena) fatua) and foxtail (Alopecurus aequalis). 10 days after sowing (when weeds reach an average of 2 leaves and soybean, radish and beet are in the initial stage of the normal growth period in the formation of leaves), 20 ml of solutions, which were made in the same way as in Example A and containing 500 ppm, 200 ppm, 100 ppm and 50 ppm of active ingredient, respectively.

Three weeks after treatment, the herbicidal effect and the degree of phytotoxicity were evaluated in the same manner as in Example A.

The results of the test are shown in Table 2 below, with h to p indicating the following weeds and crops:

h Hedgehog (Echinochloa crus-galli) i Tree frog (Digitaria adscendens) j Eleusina indica k Green grass (Setaria viridis) Deaf cves (Avena fatua) m Feathertail (Alopecurus aequalis) n Soybean (Glycine) o Radish (Raphanus) (Beta)

TABLE 2

compound number amount of active substance kg / ha h herbieid effect of weeds i j · k 1 phytotoxicity of useful plant me p 1 0.5 10 10 10 10 10 10 0 0 0 0.2 10 10 10 10 10 10 0 0 0 0.1 10 10 10 10 10 10 0 0 0 0.05 10 10 10 10 10 10 0 0 0 2 0.5 10 10 10 10 10 10 0 0 0 0.2 10 10 10 10 10 10 0 0 0 0.1 10 10 10 10 10 10 0 0 0 0.05 10 10 10 10 10 10 0 0 0 3 0.5 10 10 10 10 10 10 0 0 0 0.2 10 10 10 10 10 10 0 0 0 0.1 10 10 10 10 10 10 0 0 0 0.05 10 10 10 10 9 10 0 0 0 4 0.5 10 10 10 10 10 10 0 0 0 0.2 10 10 10 10 10 10 0 0 0 0.1 10 9 9 9 9 10 0 0 0 0.05 9 9 9 9 8 9 0 0 0 37 0.5 10 10 10 10 10 10 0 0 0 0.2 10 10 10 10 10 10 0 0 0 0.1 10 10 10 10 10 10 0 0 0 0.05 10 10 10 10 10 10 0 0 0 38 0.5 10 10 10 10 10 10 0 0 0 0.2 10 10 10 10 10 10 0 0 0 0.1 10 10 10 10 10 10 0 0 0 0.05 . 10 10 10 10 10 10 0 0 0 39 0.5 10 10 10 10 10 10 0 0 0 0.2 10 10 10 10 10 10 0 0 0 0.1 10 10 10 10 10 10 0 0 0 0.05 10 10 10 10 10 10 0 0 0 29 0.5 10 10 10 10 10 10 0 0 0 0.2 10 10 10 10 10 10 0 0 0 0.1 10 10 10 10 10 10 0 0 0 0.05 10 10 10 10 10 10 0 0 0 41 0.5. 10 10 10 10 10 10 0 0 0 0.2 10 10 10 10 10 10 0 0 0 0.1 10 10 10 10 10 10 0 0 0 0.05 10 10 10 10 10 10 0 0 0

compound number amount of active substance kg / ha h herbicidal effect of weeds i j k 1 phytotoxicity of useful plant m n 0 p 42 0.5 10 10 10 10 10 10 0 0 0 0.2 10 10 10 10 10 10 0 0 0 0.1 10 10 9 9 8 9 0 0 0 0.05 9 , 9 8 8 7 8 0 0 0 44 0.5 10 10 10 10 10 10 0 0 0 0.2 10 10 10 10 10 10 0 0 0 0.1 10 10 10 10 10 10 0 0 0 0.05 10 10 9 9 9 9 0 0 0 48 0.5 10 10 10 10 10 10 0 0 0 0.2 10 10 10 10 10 10 0 0 0 0.1 10 10 10 9 9 10 0 0 0 0.05 9 10 9 8 7 9 0 0 0 49 0.5 10 10 10 10 10 10 0 0 0 0.2 10 10 10 10 10 10 0 0 0 0.1 10 10 9 9 8 10 0 0 0 0.05 9 9 8 8 7 9 0 0 0 50 0.5 10 10 10 10 10 10 0 0 0 0.2 10 10 10 10 10 10 0 0 0 0.1 10 10 10 10 10 10 0 0 0 0.05 10 10 10 10 10 10 0 0 0 51 0.5 10 10 10 10 10 10 0 0 0 0.2 10 10 10 10 10 10 0 0 0 0.1 10 10 10 10 9 10 0 0 0 0.05 9 10 9 9 8 9 0 0 0 52 0.5 10 10 10 10 10 10 0 0 0 0.2 10 10 10 10 10 10 0 0 0 0.1 10 10 10 10 10 10 0 0 0 0.05 10 10 10 10 9 10 0 0 0 55 0.5 10 10 10 10 10 10 0 0 0 0.2 10 10 10 10 10 10 0 0 0 0.1 10 10 10 10 10 10 0 0 0 0.05 10 10 9 9 9 9 0 0 0 57 0.5 10 10 10 10 10 10 0 0 0 0.2 10 10 10 10 10 10 0 0 0 0.1 10 10 9 9 9 10 0 0 0 0.05 9 9 8 8 8 9 0 0 0 58 0.5 10 10 10 10 10 10 0 0 0 0.2 10 10 10 10 10 10 0 0 0 0.1 10 9 9 9 9 10 0 0 0 0.05 9 8 8 9 7 9 0 0 0 59 0.5 10 10 10 10 10 10 0 0 0 0.2 10 10 10 10 10 10 0 0 0 0.1 10 10 10 10 10 10 0 0 0 0.05 10 9 10 9 9 9 0 0 0 16 0.5 10 10 10 10 10 10 0 0 0 0.2 10 10 10 10 10 10 0 0 0 0.1 10 10 10 10 10 10 0 0 0 0.05 10 10 9 9 9 10 0 0 0 60 0.5 10 10 10 10 10 10 0 0 0 0.2 10 10 10 10 10 10 0 0 0 0.1 10 9 10 9 9 9 0 0 0 0.05 9 7 9 9 8 9 0 0 0 61 0.5 10 10 10 10 10 10 0 0 0 0.2 10 10 10 10 10 10 0 0 0 0.1 9 9 9 9 9 10 0 0 0 0.05 9 8 8 8 8 9 0 0 0 63 0.5 10 10 10 10 10 10 0 0 0 0.2 10 10 10 10 10 10 0 0 0 0.1 10 9 10 10 9 9 0 0 0 0.05 9 8 9 9 9 9 0 0 0

compound number amount of active substance kg / ha h herbicidal effect of weeds i j k 1 phytotoxicity of useful plant m η o p 17 0.5 10 10 10 10 10 10 0 0 0 0.2 10 10 10 10 10 10 0 0 0 0.1 10 9 10 10 10 10 0 0 0 0.05 9 8 9 9 9 9 0 0 0 64 0.5 10 10 10 10 10 10 0 0 0 0.2 10 10 10 10 10 10 0 0 0 0.1 10 9 10 10 10 9 0 0 0 0.05 10 8 9 9 9 9 0 0 0 65 0.5 10 10 10 10 10 10 0 0 0 0.2 10 10 10 10 10 10 0 0 0 0.1 10 8 10 10 9 9 0 0 0 0.05 9 7 9 9 8 8 0 0 0 67 0.5 10 10 10 10 10 10 0 0 0 0.2 10 10 10 10 10 10 0 0 0 0.1 10 8 10 9 9 9 0 0 0 0.05 9 7 9 9 8 8 0 0 0 68 0.5 10 10 10 10 10 10 0 0 0 0.2 10 10 10 10 10 10 0 0 0 0.1 10 10 10 10 9 10 0 0 0 0.05 10 9 9 9 9 9 0 0 0 20 May 0.5 10 10 10 10 10 10 0 0 0 0.2 10 10 10 10 10 10 0 0 0 0.1 10 10 10 10 10 10 0 0 0 0.05 10 9 9 9 9 9 0 0 0 21 0.5 10 10 10 10 10 10 0 0 0 0.2 10 10 10 10 10 10 0 0 0 0.1 10 10 10 10 10 10 0 0 0 0.05 10 9 9 9 9 10 0 0 0 70 0.5 10 10 10 10 10 10 0 0 0 0.2 10 10 10 10 10 10 0 0 0 0.1 10 10 9 10 10 10 0 0 0 0.05 9 9 9 9 9 9 0 0 0 71 0.5 10 10 10 10 10 10 0 0 0 0.2 10 10 10 10 10 10 0 0 0 0.1 10 9 9 10 9 9 0 0 0 0.05 9 9 9 9 9 9 0 0 0 24 0.5 10 10 10 10 10 10 0 0 0 0.2 10 10 10 10 10 10 0 0 0 0.1 10 10 10 10 10 10 0 0 0 0.05 10 9 9 9 9 10 0 0 0 25 0.5 10 10 10 10 10 10 0 0 0 0.2 10 10 10 10 10 10 0 0 0 0.1 10 10 10 10 10 10 0 0 0 0.05 10 9 9 9 9 10 0 0 0 72 0.5 10 10 10 10 10 10 0 0 0 0.2 10 10 10 10 10 10 0 0 0 0.1 10 10 10 10 10 10 0 0 0 0.05 10 9 10 10 9 9 0 0 0 27 Mar: 0.5 10 10 10 10 10 10 0 0 0 0.2 10 10 10 10 10 10 0 0 0 0.1 10 10 10 10 10 10 0 0 0 0.05 10 10 10 10 9 9 0 0 0 73 0.5 10 10 10 10 10 10 0 0 0 0.2 10 10 10 10 10 10 0 0 0 0.1 10 10 10 9 10 9 0 0 0 0.05 10 9 9 9 9 9 0 0 0 23 0.5 10 10 10 10 10 10 0 0 0 0.2 10 10 10 10 10 10 0 0 0 0.1 10 10 10 10 10 10 0 0 0 0.05 10 9 9 9 9 9 0 0 0

compound number amount of active substance kg / ha h herbicidal effect of weeds i j к 1 phytotoxicity of the useful plant mnu p 76 0.5 10 10 10 10 10 10 0 0 0 0.2 10 10 10 10 10 10 0 0 0 0.1 10 10 10 10 10 10 0 0 0 0.05 10 9 9 9 9 9 0 0 0 78 0.5 10 10 10 10 10 10 0 0 0 0.2 10 10 10 10 10 10 0 0 0 0.1 10 10 10 10 10 10 0 0 0 0.05 10 9 9 9 9 9 0 0 0 comparative 0.5 10 10 10 10 9 10 0 0 0 merge- 0.2 9 10 9 9 7 10 0 0 0 A-2 0.1 7 8 6 7 5 8 0 0 0 0.05 5 5 5 6 4 6 0 0 0 C-1 0.5 10 10 9 10 9 10 0 0 0 0.2 10 9 6 9 6 9 0 0 0 0.1 7 5 3 6 3 6 0 0 0 0.05 3 2 1 3 1 3 0 0 0

Example C evaluation of the effect against further growth (based on inoculated control plants)

Test for herbicidal and antifungal growth (Agropyron tsukushiense)

The rice fields where tufts (Agropyron tsukushiense) are present in tufts are divided into 1 m ² parcels. 100 ml of solutions prepared in the same manner as described in Example A and containing 1000 ppm, 500 ppm, 200 ppm and 100 ppm of active ingredient, respectively, are applied uniformly to the leaves of each of the plots (Agropyron tsukushiense). The herbicidal effect is evaluated 20 days after treatment in the same manner as in Example A. Furthermore, 40 and 60 days after treatment, the effect against further growth of the wheat is evaluated according to the following scale:

100% (total prevention of further growth) of at least 90 ° / o but less than 100% at least 80 ° / o but less than 90% at least 70 but less than 80% at least 60% but less than 70 ° / o ° / o but less than 60% at least 40 ° / o but less than 50% at least 30 ° / o but less than 40% at least 20 ° / o but less than 30% at least 10% but less than 20 ° / o

0 'less than 10% (no effect to prevent further growth)

The test results are shown in Table 3 below:

compound

C.

TABLE 3 amount of active substance kg / ha herbicidal effect against further growth days after. treatment 40 days after treatment 60 days after treatment

1 1.0 10 0.5 10 0.2 10 0.1 9 29 1.0 10 0.5 10 0.2 10 0.1 9 58 1.0 10 0.5 10 0.2 10 20 May 1.0 10 0.5 10 0.2 10 0.1 9 21 1.0 10 0.5 10 0.2 10 0.1 9 24 1.0 10 0.5 10 0.2 10 0.1 9 74 1.0 10 0.5 10 0.2 10 0.1 9 77 1.0 10 0.5 10 0.2 10 0.1 9 compares- 1.0 10 combining 0.5 7 chenina 0.2 4 B-l 0.1 1 compares- 1.0 10 combining 0.5 9 chenina 0.2 6 D-l 0.1 3

10 10 10 10 10 10 8 7 10 10 10 10 10 10 8 7 10 10 10 10 10 9 10 10 10 10 10 10 9 8 10 10 10 10 10 10 8 8 10 10 10 10 10 10 8 7 10 10 10 10 10 9 9 8 10 10 10 10 10 10 8 7 10 6 6 3 3 0 0 0 10 7 7 2 3 0 0 0

Example D

Test for herbicidal and antifungal activity (Cynoden dactylon)

The above-mentioned fields, in which widespread Cynodon dactylon] is widespread, are divided into 1 m2 parcels. The active ingredient is used in the same amount as in Example C to treat ringworm.

In the same manner as in the previous Examples A to C, the herbicidal effect was evaluated 20 days after treatment. 40 and 60 days after treatment, the effect against further growth is evaluated.

The test results are shown in Table 4 below:

TABLE 4

compound number amount of active substance kg / ha herbicidal effect effect against further growth 20 days after treatment 40 days after treatment 60 days after treatment 1 1.0 10 10 10 0.5 10 10 10 0.2 10 10 10 0.1 8 7 5 2 1.0 10 10 10 0.5 10 10 10 0.2 10 10 8 0.1 10 8 7 4 1.0 10 10 10 0.5 10 10 10 0.2 10 10 9 0.1 9 8 6 37 1.0 10 10 10 0.5 10 10 10 0.2 10 10 8 0.1 9 8 7 20 May 1.0 10 10 10 0.5 10 10 10 0.2 10 9 8 0.1 9 9 7 21 1.0 10 10 10 0.5 10 10 10 0.2 10 9 8 0.1 9 8 7 75 1.0 10 10 10 0.5 10 10 10 0.2 10 9 8 0.1 9 8 7 79 1.0 10 10 10 0.5 10 10 10 0.2 10 9 8 0.1 9 7 6 compares- 1.0 10 9 5 combining 0.5 8 5 2 chenina 0.2 5 2 0 B-l 0.1 4 0 0 compares- 1.0 10 10 7 combining 0.5 9 7 5 chenina 0.2 7 3 0 D-l 0.1 5 1 0 Also for other compounds except those The following examples illustrate in more detail how which were used in the examples A to D, method of production of compounds of formula I, was found, that they have in the same low which are used as active ingredients in quantities, used in compositions according to the invention. A < to D, excellent herbicidal activity Examples illustrating Production method and that i after a long time period have Substances: ability to prevent regeneration persistent grassy weeds. Example 1

25.4 g of 4- (4-trifluoromethylphenoxy) phenyl are added to 150 ml of absolute acetonitrile, and then 28.7 g of 2-benzyloxyethyl 2-bromopropionate and 14.5 g of anhydrous potassium carbonate are added. The mixture was then heated to reflux for 4 hours with good stirring. After completion of the reaction, the residue was distilled off under reduced pressure.

Toluene was added to the residue, and the toluene layer was washed successively with 1% aqueous sodium hydroxide and water. After distilling off toluene under reduced pressure to yield as a reaction product of 2-benzyloxyethyll2- [4- (4 - rifluormethylfenoxyjfenoxyjpropíonát colorless viscous product in a yield of 41 g. N D ² 0 = 1.5300.

Example 2

Cl

Cfi ₃ o-θ- oc w -co - (^ ο-σ ^ θ-Γ (2)

30.6 g of 4- (3,5-dichloro-2-pyridyloxy) phenoxy sodium salt and 30.5 g of 2- (4-fluorobenzyloxy) ethyl 2-chloropropionate are added to 100 ml of dimethylformamide and the mixture is heated to 70 DEG-80 DEG C. After cooling to room temperature, the reaction solution is poured into 300 ml of water and then extracted with ether, and the ether layer is washed successively with aqueous 1% sodium hydroxide solution and water and then dried to remove After distilling off the ether, 38 g of pale yellow viscous oily 2- (4-fluorobenzyloxy) ethyl 2- [4- (3,5-dichloro-2-pyridyloxy) thenoxy] propionate are obtained in the form of the final product. 1,5643.

Example 3

In an analogous manner to that described in Examples 1 and 2, 2- (2,6-dichlorobenzyloxy) ethyl 2- [4- (4-difluoromethylphenoxy) phenoxy] propionate of formula:

Mp 51-53 ° C.

EXAMPLE 4 Examples 1 and 2 produce 1-methyl-2-benzyloxyethyl 2- [4- (3,5-dichloro-2-pyridylloxy) phenoxy] propionate of formula

In an analogous manner to that described in

of Example 1 or 2, but using the starting materials listed in the following table, the other compounds of the present invention are synthesized and listed in the following table:

nD2 = 1.5710.

Example 5

In the same way as described in the appendix

-w 'cd

гД o>

<

E-q П PQ <

H χ з

TJ О-4 Он φ> ω

Φ φ ί-4

Φ Φ WITH 4 Φ 4 X3 Φ 4 φ 4 ^ 4 4 CM СЧ φ СО what WHAT οο ~ Д 4 U, » ^ 4 Φ Рч O Ф 1 ó Φ Φ 4 o Λ phi ⁵³¹ cd 1 ο Φ φ 4 ο Φ φ 1 ί * '“' 1 'Φ X' Φ _Ρ —4 ^Ο _ | 4 sjí ο φ φ 4 φ 4 φ 4 Φ 1 Φ г — 4 ς ~ * with Q— ( оф «♦ H оф <4-4 οφ <4—4 <α й ° φ ω ω ° 5 ° Φ ω «4-4 Ξ ο ° Φ ο Ξ ο οφ Ο • P ω СП Τ 'ν> V3 СП '-' ω φ СЛ φ ω Φ СЛ φ ř-4 4- · » r— < 'here >. X 'CD * '« X 'φ X 'Φ Eť' Φ ° C φ 'φ φ 'φ > S X 'Φ φ «4-4 'φ φ <4-4 'Φ φ <4-4 'Φ φ <4—4 1 O 4 O Φ O Ф о й ο Φ ο ο Φ ο Φ ο Φ φ Φ Φ φ Φ I.E Φ I.E α Φ I.E Φ Χ χ * Ό Д τι Φ I.E Д I.E > чТЗ > S I.E >> | Φ 4 Φ O Φ O ф о φ ο φ ο ο Ο φ ο φ Ο φ ο χ ο X ο X Ο X ’Φ <4—1 <4-4 ω 0-4 СЛ он ω <4-4 СЛ <4-4 СЛ ι СЛ <4Μ СЛ <4-4 СЛ <4-1 СЛ ο <η ο ω Ο ώ ο

In the same manner as described in Examples 1 and 2, the compounds listed in the following examples were prepared using the corresponding starting materials:

Example 20

2-Benzyloxyethyl-2- [4- (5-trifluoromethyl-2-pyridyloxy) phenoxy] propionate

Mp 44-47 ° C.

Example 21

2- (2-Fluorobenzyloxy) ethyl 2- [4- (5-trifluoromethyl-2-pyridyloxy] phenoxy] propionate

Mp 46-48.5 ° C.

Example 22

2- (4-chlorobenzyloxy) ethyl 2- [4- [5-trifluoromethyl-2-pyridyloxy] phenoxy] propionate n _D 20 = 1.5350.

Example 23

2- (4-methoxybenzyloxy) ethyl 2- [4- (5-trifluoromethyl-2-pyridyloxy) phenoxy] propionate; n _D 20 = 1.5335.

Example 24

1-methyl-2-benzyloxyethyl-2- [4- (5-trifluoromethyl-2-pyridyloxy) phenoxy] propionate n _D 20 = 1.5224.

Example 25

3-Benzoloxyphyl-2- [4- (5-difluoromethyl-2-pyridyloxy) phenoxy] propionate p20 = 1.5245.

Example 26

2-Benzyloxyethyl-2- [4- (3-morpholin-S-nitro-2-pyridyloxy) phenoxy] propionate

Example 27

2-Benzyloxyethyl 2- [4- (3-chloro-5-difluoromethyl-2-pyridyloxy] phenoxy] propionate

Example 28

2- [2-Methoxyoxybenzyloxy] ethyl 2- [4- (3,5-dichloro-2-pyridyloxy] phenoxy] propionate

Example 29

2- (2-Fluorobenzyloxy] ethyl 2- [4- (4-trifluoromethylphenoxy) phenoxy] propionate of formula

F

(291 nD ^M = 1.5235).

Example 30

2-Benzyloxyethyl-2- [4- (5-trifluoromethyl-2-yridyloxy) phenoxy] propionate of the formula

O

CH ₃ o осн-с-о-с ^ сн _£ о-сн.

Mp 44-47 ^° C.

Examples 31 to 79

(30) In the above examples, the compounds of formula (I), which are listed in the following Table 5, were prepared.

¹ analogous manner as described ·

TABLE 5

Ar R1 R ² m Xa physical data

-O H H Cl H H W-O H H CFa c-tf- H H N0 ₄ H H H H —CH3 H v-O H - -CHs ^r 3 ^c 7Z H H v- ~ F H H v ~ O- H H , ^N0 * H H H H

H n _D 20 1.5322

1 H in _D ²⁰ 1.5518 1 H n _D ² 0 1.5696 1 H m _D ²⁰ 1.5805 1 H .¾ ²⁰ 1.5397 1 H Md ² ° 1.5450 2 H mD ²⁰ 1.5268 1 H oId ²⁰ 1.5260 1 H ®d20 1,5266 1 2-F ií1d ² 0 1.5 2 35 1 4-F 01d2 ° 1.5214 1 2-C1 [.alpha.] D @ ²⁰ = 1.536 DEG 1 2-C1 nD ² ° 1.5550 1 4-C1 n _D ²⁰ 1.536 °

Ar

R1 R2 n X _a

14-C1

14-C1

14-C1

2,4-012

3,4-012

12-СНз

13-NO2

4-ОСНз

2Η

14-01

14-Br

1H

12-01

1H

1H physical data «и ²⁰ 1.5380 in _D ²⁰ 1.5450 in _D 20 1.5559 n _D ² ° 1.5422 n _D ²⁰ 1.5428 in _D 20 1.5305 <n _D 20 1.5436 η _υ ² «1.5343 m _n ² « 1.5440 n _D ²⁰ 1.5875 n _D ²⁰ 1.5450 in _D 20 1.5650 n _D ²⁰ 1.5718

mp 59-61 ° C n _D ²⁰ 1.5715 Example ArR no

-

60Cl -

O ^ Nh

R ² m Xa physical data H 2 H , n _D 20 1.5721 H 1 H oil H 1 3-MO2 oil H 1 2-F mp 54-57 ° C H 1 2-CI mp 64-66 ° C

H 1 4-C1 η _η 20 1.5803 H 1 4-C1 oil H 1 3-NO2 , n _D 2 &gt; 1.5845 H 1 2-СНз mp 83-85 ° C H 1 2,4-012 oil H 1 3,4-012 η ₀ 2θ 1.5900 H 1 2,6-012 n _D 20 1.5915 H 1 4-ОСНз -n _D 20 1.5735 H 1 4-Вг n _D 20 1.5870

37 229 example number Ar R ¹ 74 H 75 H 76 H 77 H 78 H 79 ^F 3 ^C O- H

83 R ² n 38 x _;) physical data СНз 1 H η ₀ 2θ 1.5254 H 1 2-СНз n _D ²⁰ 1.5273 H 1 2-C1 n _D ²⁰ 1.5349 H 1 4-Br in _D ²⁰ 1.5440 H 1 3-NO2 n _D ²⁰ 1.5428 H 1 2.4-C12 n _D 2 ° 1.5424

The following examples illustrate the preparation of the novel compounds of formula (III) which are used as starting materials for the process of the invention.

EXAMPLE 80 [α] CH-C-O-CH 2 CH 2 O _from OC [compound of formula III]

15.2 g of bemzyloxyethanol and 10.6 g of triethylamine are dissolved in 150 ml of toluene and the resulting solution is cooled to -5 ° C. While stirring, a solution of 21.6 g of 2-bromopropioinyl bromide in 30 ml of toluene is added dropwise at -5 ° C to 0 ° C. The reaction mixture is then kept at room temperature for a further 2 hours and then washed successively with 1% sodium hydroxide solution and water, after which the toluene layer is dried and filtered. Toluene was distilled off under reduced pressure to give 2-benzyloxyethyl-2-bromopropionate in 26.7 g (n _D ²⁰ · ⁵ = 1.5182) as reaction product.

The intermediates of formula (III) of the present invention, which are listed in Table 6 below, are obtained in a similar manner as described above.

CH ₃ OR ¹ 1}

Z'-CH-CO-CH (СН ₂ ) _and -O-СН

TABLE 6

(А (III)

From ¹ R ¹ R ² n Xa physical constants Br H H 1 H n _D ²⁰ · ⁵ 1.5182 Br H H 1 2-F n _D ²⁰ 1.5038 Cl H H 1 4-F n _D ²⁰ 1.5004 Br H H 1 4-F n _D ²⁰ 1.5040 Br H H 1 2-C1 n _D ²⁰ · ⁵ 1.5302 Br H H 1 4-C1 n _D ²⁰ 1.5289 Cl H H 1 4-Br n _D ²⁰ - ⁵ 1.5321 Br H H 1 4-Br n _D ²⁰ · ⁵ 1.5434 Br H H 1 2-СНз n _D ²⁰ 1.5186 Br H H 1 2-ОСНз n _D ²⁰ ' ⁵ 1.5260 Br H H 1 3-NO2 n _D ²⁰ 1.5394 Br H H 1 2,4-012 n _D ²⁰ 1.5395 Br H H 1 3,4-012 n _D ²⁰ 1.5409 Cl H H 1 2,6-012 n _D ²⁰ 1.5412 Br СНз H 1 Η n _D ^20-5 1.5100 Br H СНз 1 Η n _D ²⁰ · ⁵ 1.5116 Br H H 2 Η n _D ²⁰ · ⁵ 1.5130 Br H H 1 4-ОСНз n _D ²⁰ · ⁵ 1.5250

OBJECT OF THE INVENTION

Claims (4)

A herbicidal composition, characterized in that it contains at least one substituted phenoxypropionate of the formula I as active ingredient. I č O-CH-C-O ti / wherein R ¹ and R ² are each independently hydrogen or C 1-6 alkyl IN carbon atoms, X is hydrogen or halo- Y —Ttebo a gene or nitro group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and n are each independently Gal (lb) number 1 or 2, and Ar is a group of formulas Ia or Ib Ar represents a group of formulas Ia or Ib wherein Y represents a trifluoromethyl group, a halogen atom or an initro group, a cyano group or an alkyl group having 1 to 6 carbon atoms, and b represents 1, 2 or 3. 2. A composition according to claim 1, wherein the active ingredient comprises at least one substituted phenoxypropionate of formula I, wherein: R ¹ and R ² are each independently hydrogen or methyl, ethyl, n-propyl, isopropyl, η-, iso-, sec- or tert-butyl, X is hydrogen, fluorine, chlorine, bromine or iodine, nitro, methyl, methoxy, ethyl, ethoxy, n-propyl, n-propoxy, isopropyl, isopropoxy or η-, iso-, sec- or tert-butyl or η-, iso-, sec- or tert-butyl, and a and n are each independently 1 or 2; Y is trifluoromethyl, fluorine, chlorine, bromine or iodine, or nitro, cyano, methyl, ethyl, propyl, isopropyl, η-, iso-, sec or tert-butyl and b is 1, 2 or 3. 3. A composition according to claim 1, wherein the active ingredient comprises at least one substituted phenoxypropionate selected from the group consisting of: 2- (4-chloro-benzyloxy) -ethyl-2- [4- (4-trifluoromethylphenoxy) phenoxy] propionate of the formula ^-CH 2> i? o-ch-c-o-o ^ o-c ^ Ф Cl 3-Benzyloxypropyl 2- [4- (4-trifluoromethylphenoxy) phenoxy] propionate of formula 2 - «- methylbenzyloxyethyl-2- [4- (4-trifluoromethylphenoxy) phenoxy] propionate of the formula l-Methyl-2-benzyloxy-ethyl 2- [4- (4-trifluoromethylphenoxy) phenoxy] propionate of the formula I ^ ³ _CH3 clay О-СН-С-О-СНС2 ^ О-СН ^ \ Х 2- (2-fluorobenzyloxy) ethyl 2- [4- (3,5-dichloropyridyloxy) phenoxy] propionate of formula 2-benzyloxy yethyl 2- [4- (3,5-dichloropyridyloxy) phenoxy] propionate of formula 1-methyl-2-benzyloxyethyl 2- [4- (3,5-dichloropyridyloxy) phenoxy] propionate of formula o-CH - CO-CH CH ₂ O-CH 2- (4-chlorobenzyloxy) ethyl 2- [4- (3,5-dichloropyridyloxy) phenoxy] propionate of the formula C 1 -phenyl-O-CH-C-O- (CH 2 qO) 4. A process for the preparation of an active ingredient according to claim 1, which process comprises treating a compound of the formula II M is an alkali metal of formula (III), or an alkali atom R ² in which Ar is as defined in 1 and III (II) in cup R ¹ , R ² , X, a and ⁿ have the meanings given in 1 a Z ¹ represents a halogen atom, optionally in the presence of an acid acceptor and optionally in the presence of a diluent at temperatures between 0 ^C and 100 ° C.