HU190852B - Herbicide compositions containing pyrimidine derivatives substituted with /chloro-acetyl/-groups as active ingredients and process for preparing the active ingredients - Google Patents

Description

The present invention relates to herbicides which contain pyrimidine compounds substituted at the 5-position (chloroacetyl) amino as an active ingredient, and to a process for the preparation of pyrimidine compounds substituted at the 5-position (chloroacetyl) amino.

The herbicides according to the invention contain as active ingredient (1.05-80% by weight of the compounds of the formula I;

Y is pyrazol-1-ylmethyl, (C 1 -C 5) alkoxy (C 1 -C 5) alkyl, (C 3 -C 5) alkenyloxy) (C 1 -C 5) alkyl, (4-methylthiazol-2-yl). ) methyl or (2-methylthiazol-4-yl) methyl;

R _{7 and} R ₅ are independently C 1-4 alkyl, C 1-4 alkoxy, or di (C 1-4 alkyl) amino.

German Patent No. 2,320,340 discloses Ν, Ν-disubstituted chloroacetamide derivatives which are useful as herbicides.

The present invention also relates to a process for the preparation of compounds of formula Ib comprising the compounds of formula I. In the general formula Ib

R ₁ and R _{1 (1} independently of one another C 1-4 alkyl, C 14 alkoxy, C 1-4 alkylthio, di (C 1-4 alkyl) amino, or N- (C 1-4 alkyl) ) -N-phenylamino, hydrogen or halogen;

R 1 is hydrogen or halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, or di (C 1 -C 4 alkyl) amino;

Y., C 1 -C 5 monohaloalkyl, C 3 -C 5 alkenyl or alkynyl optionally monosubstituted with halo, (C 1 -C 4 alkoxy) optionally monosubstituted with C 1 -C 4 alkoxy - (C 1 -C 3 alkyl) a group, [halo (C3-C6 cycloalkyl) - (C1-C4 alkyl), (C3-C5 alkenyloxy) - (C1-C3 alkyl), or (C3-C5 alkynyloxy) - (C 1 -C 3 alkyl); -CH-COY wherein Y is (C 1 -C 4) alkoxy or di (C 36 -alkenyl) amino; A 1-indazolyl or 1-triazolyl group or a five membered heterocyclic group which is attached to the -CH 1 group by a carbon atom and which contains one sulfur atom or one nitrogen atom and one oxygen atom or sulfur atom or one oxygen atom and two nitrogen atoms, or 2-pyrimidinyl and the heterocyclic ring is optionally 1 Monosubstituted with C 4 alkyl.

A preferred group of active compounds of formula (I) are those compounds having the formula

_R7 and _Rs one C 1-4 alkoxy or di (C1 -C4 alkilj-amino.

Preferably R ₇ and R _{x are C} 1-4 alkoxy, preferably methoxy, ethoxy, isopropoxy or η-butoxy, especially isopropoxy.

R _{7 and} R as di- (1-4C-amino group preferably include a dimethylamino group.

When R ₇ and R _{N are C} 1 -C 4 alkyl, it is preferably methyl.

Y., preferably represents, for example, 1,2,4-triazol-1-yl, 2-methyl-1,3,4-oxadiazol-5-yl, 3-methyl-1,2,4-oxadiazol-5-yl, methyl-isoxazol-5-yl, 2-methyl-thiazol-4-yl, 2-thienyl, 2-pyrimidinyl or 1-pyrazolyl, in particular the latter.

According to the invention, the compounds of formula (1b) are prepared by:

(a) in a compound of formula (II):

R 1, R 1, 1, R 1, and Y 1 are as defined above - the hydroxyl group of the N- (hydroxyacetyl) group is replaced by chlorine in a known manner;

b) a compound of formula III wherein R 1 is. R '' and R '' as defined above, with a compound of formula IV, wherein Y is _a group L and a leaving group which may be cleaved under N-alkylation reaction conditions, are N-alkylated; obsession

c) (V) compounds of the formula: - wherein R ,,, R _{1 (I,} R _h and Y are as defined above - chloroacetyl chloride in N-acylation.

Process a) is carried out in the usual manner, under known reaction conditions for the substitution of a hydroxy group with a chlorine atom.

This substitution may be effected, for example, by treating a compound of formula (II) with a chlorinating agent such as thionyl chloride to carry out similar reactions under reaction conditions known per se.

In a variant of the chlorination process, the compounds of formula II are first converted to the corresponding sulfonyloxy derivatives, for example by O-sulfonation using a sulfonyl halide, followed by nucleophilic substitution of the sulfonyloxy group with the chlorine atom of the sulfonyloxy group. to the desired compounds of formula (I).

Chloride anions required for nucleophilic substitution are provided, for example, by alkali metal chlorides such as sodium chloride, quaternary tetrabutylammonium chloride or 4- (dimethylamino) pyridine hydrochloride reagents, preferably in a dichloromethane or dichloromethane system. wherein the organic phase is, for example, a hydrocarbon such as toluene in the presence of a suitable phase transfer catalyst, preferably under heating, for example at 40-120 ° C.

Process b) may be carried out in conventional manner under known reaction conditions for N-alkylation of the azamides. The reaction is preferably carried out in a solvent inert to the reaction conditions, such as dimethoxyethane or acetonitrile or in an aqueous-organic biphasic system in the presence of a phase transfer catalyst.

In the general formula (IV), L is a suitable meaning

190,852 chlorine or bromine, or a sulfonyloxy group of an organic sulfonic acid, such as mesyloxy or p-tosyloxy.

The compounds of formula (III) are preferably used in salt form, in particular in the form of the alkali metal salt, for example the sodium salt. These salts are prepared in a conventional manner by reacting a compound of formula (III) with a base such as an alkali metal amide, anhydride, hydroxide or alcoholate.

Process c) can be carried out under known conditions for the N-chloro acetylation of the amines. The reaction is conveniently carried out in the presence of an acid acceptor such as potassium carbonate.

The compounds of formula (I) are isolated from the reaction mixtures in which they are formed by work-up according to known methods.

The compounds of formula (Π), (III) and (V) are novel. They may be prepared in conventional manner, for example starting from a suitable 5-aminopyrimidine of formula (VI) wherein Ar is as defined above.

Compounds of formula (II) may be prepared by reacting a compound of formula (VI) with acetoxyacetyl chloride and then hydrolyzing the resulting acetoxyacetamide.

Compounds of formula (III) may be prepared by reacting a compound of formula (VI) with chloroacetyl chloride.

Compounds of formula (V) may be prepared by N-alkylation of compounds of formula (VI). The alkylation may be carried out in a conventional manner, directly, with the appropriate alkylating agent or, where appropriate, reductively, on a Schiff base or over a period of time.

Some of the compounds of formula VI are known.

The novel compounds of formula VI may be prepared by analogous methods to known procedures. For example, 5-amino-4,6-dimethylpyrimidine, a novel compound, can be prepared by catalytically hydrogenating [4,6-dimethyl-2-thiopyrimidin-5-ylazo) benzene in the presence of Raney nickel.

A number of other novel compounds of formula (VI) can be prepared from 2,4-dihydroxy-6-methylpyrimidine or 4,6-dihydroxypyrimidine by various reactions, respectively. Examples of such reactions include:

nitration (introduction of NO _{2 with} nitric acid, for example), chlorination (substitution of the hydroxy group with a chlorine atom such as phosphorus trichloride), alkoxylation (substitution of the chlorine atom with an alkoxy group, alkali metal alcoholate), hydrogenation (nitro group reduction / hydrogenation) In the presence of C), amination (substitution of the chlorine atom with an amino group), elimination of the chlorine atom (by hydrogenation in the presence of Pd / C).

If the preparation of the starting materials is not described, they are known either by known methods or by methods similar to those described herein or by known methods.

The compounds of formula I are useful in controlling or modifying plant growth. By plants are meant germinating seeds, outgrown seedlings and mature plants, including underground parts of plants.

The compounds of formula (I), as mentioned above, can be used primarily as herbicides to combat damage caused by both monocotyledonous and dicotyledonous weeds, such as in experiments against Lepidium sativum, Avena sativa, Agrostis alba and Lolium perenne. kg / ha applied before or after plant growth. In view of their herbicidal activity, the compounds of the formula I are suitable for controlling dicotyledonous and grass weeds, as demonstrated by further experiments with the compounds. The application rate () is 2-5.0 kg, e.g. 0.2, 1.0 and 5.0 kg active ingredient / hectare experimental dose for dicotyledonous weeds such as Amaranthus retroflexus, Capsella bursa pastoris, Chenopodium album, Stellaria media. , Senecio vulgaris and Galium aparine, as well as weeds such as Agropyron repcns, Agrostis alba, Alopecurus myosuroides, Apera spica venti, Avena fatua, Echinochloa crus-galli, Setaria italica. Poa annua, Panicum miliaceum, Eleusine indica, Diguitaria sanguinalis and Sorghum halepense.

The compounds of formula I are relatively less toxic to crops such as grasses such as small grains such as winter cereals or rice or cereals and especially broadleaf crops such as cotton, sugar beet, potato, sunflower, rapeseed or flax as weeds. Compounds of formula (I) may therefore also be proposed as selective herbicides in the crop field.

The compounds of formula (I) have a very long duration of action, which is essential for their practical use, and is surprising, inter alia, from the experience with the compounds of U.S. Patent 4,282,028.

When used for general and selective weed control, the amount of the compound of formula (I) employed will vary depending on the particular crop present when used for selective weed control and other variables such as the compound employed, the mode of application, depending on the treatment conditions. Suitable application rates can be determined by those skilled in the art using routine methods, or by comparing the effects of the compounds of formula (I) with standard compounds of known application rates, for example, in greenhouse experiments. However, in general, satisfactory results are obtained when the compounds are applied in a ratio of from about 0.1 to about 5 kg / ha, preferably from about 0.2 to about 4 kg / ha, particularly from 0.5 to 3 kg / ha, repeated as necessary. When used in a crop area, the application3

Preferably, the application rate of 190.852 should not exceed 3 kg / ha. For pre-emergence application, the particularly preferred application rate is 0.5-1.5 kg active ingredient / hectare, and after emergence this particularly preferred application rate is 1.0-3.0 kg active ingredient / ha.

The compounds of formula (I) may be used as herbicides in admixture with acceptable diluents for herbicide and preferably used as such. Suitable herbicides comprise from 0.05 to 80% by weight of the active ingredient, from 0 to 20% by weight of a herbicide acceptable surfactant and from 1 to 99.95% by weight of a solid or liquid diluent. Sometimes the proportion of surfactant relative to the active ingredient may need to be increased by simply mixing the surfactant into the formulation or mixing it in a container. Uses of herbicides generally contain 0.0125% by weight of active ingredient. Of course, depending on the intended use and the physical properties of the compound, the active ingredient level can be lower or higher. Concentrated forms of herbicides which need to be diluted before use generally contain from 2 to 80% by weight, preferably 10 to 50% by weight, of the active ingredient.

Suitable formulations of the compounds of formula I include powders, granules, spheres, suspension concentrates, wettable powders, emulsifiable concentrates. They are prepared in conventional manner, for example, by mixing the compounds with diluents. Specifically, liquid formulations may be prepared by mixing the components, finely divided solid formulations by mixing and typically grinding, suspensions by wet milling, and granulating and sphericals by spraying or spraying the active ingredient onto a preformed particulate carrier.

Alternatively, the compounds of formula (I) may also be used in a micro-enclosed form.

In herbicides, acceptable herbicide additives may be used to enhance the performance of the active ingredient and to prevent foaming, aggregation and corrosion.

Surfactants used for weed control are those that provide emulsifiability, dispersibility, wettability, dispersibility and other surface modifying properties of the agent. Examples of such surfactants are sodium lignin sulfonate and lauryl sulfate.

The diluents used are liquid or solid herbicide-tolerant substances used to dilute a concentrated substance to the application or required strength. Such diluents for powders or granules include talc, kaolin or diatomaceous earth, liquid concentrate forms such as a hydrocarbon such as xylene or an alcohol such as isopropanol and liquid application forms including water or diesel oil.

The herbicides of the present invention may also be mixed with other compounds having biological activity, for example, compounds having a similar or complementary herbicidal activity, or compounds having a neutralizing, antifungal or insecticidal action.

The herbicides according to the invention and the preparation of the active compounds are illustrated in the examples.

Herbicides

Example A)

A wettable powder is a portion of a compound of formula (I). for example, the compound of Example 3 is mixed with 25 parts of synthetic finely divided silica, 2 parts of sodium lauryl sulphate, 3 parts of sodium lignin sulphonate and 45 parts of finely divided kaolin, and the mixture is milled to a size of about 5 microns. . The wettable powder thus obtained is diluted with water before use to form a spray liquid of the required concentration.

Example B)

Emulsion concentrate is a portion of a compound of formula I, such as the compound of Example 3, 50 parts of xylene, 15 parts of dimethylformamide, and 10 parts of an emulsifier (e.g., ATLOX 4851 Bt, from Atlas Chemie GmbH, mixture) is thoroughly mixed until a homogeneous solution is obtained. The resulting emulsion concentrate is diluted with water before use.

Example C)

Granules are added in kg of a compound of formula I, such as the compound of Example 3, in 15 liters of dichloromethane.

dissolved. The solution was then added to 95 kg of granular attapulgite and mixed thoroughly, and the solvent was evaporated under reduced pressure. Example D) Wettable powder Example 3 801% kaolin 101% Sodium lauryl sulfate 2% Sodium ligninsulfonate 3% synthetic silica powder 5% 100% The spray liquors used in the efficacy studies are: wettable powder of the following composition water prepared by dilution: kaolin 641% Celite 400 2t% Sodium lauryl sulfate 3% Polyphone O (lignin derivative 5% agent 26% Preparation of the active compounds

/. Example [Procedure a]

N-propargyl-N- (4,6-dimethyl-2- (dimethylamino) pyrimidin-5-yl) choroacetamide

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8.0 g of N-propargyl-N- (4,6-dimethyl-2- (dimethylamino) pyrimidin-5-yl) -hydroxyacetamide, 3.7 g of 4-dimethylamino-pyridine and 100 ml of dry of methylene chloride in a sulfonation flask. To the above mixture was added dropwise 3.43 g of mesyl chloride dissolved in 30 ml of dry methylene chloride. The temperature of the reaction mixture rises from 22 ° C to 33 '' C. The mixture was refluxed for 34 hours, then cooled and diluted with water. The organic layer was separated, dried over anhydrous sodium sulfate and evaporated. The oily residue was chromatographed on silica gel with diethyl ether-hexane (1: 1) to give the title compound, mp 108-110 ° C.

Example 2 [Process b]

N-propargyl-N- (4,6-dimethyl-pyrimidin-5-yl) choroacetamide

A mixture of 5.0 g (0.025 mol) of N- (4,6-dimethylpyrimidin-5-yl) chloroacetamide and 1.0 g of tetrabutylammonium chloride was dissolved in 150 ml of dichloromethane and 6.0 propargyl bromide at 8 ° C. After cooling to 15 ° C, 15 ml of 50% aqueous sodium hydroxide solution was added dropwise while the temperature gradually increased to 20 ° C. The reaction temperature was maintained at 18-20 ° C by cooling. The reaction mixture was stirred for 2.5 hours and then diluted with 100 ml of water. The organic layer was separated and dried over anhydrous sodium sulfate. The dried solution was evaporated to a brown powder, which was chromatographed on silica gel with diethyl ether _(Rf = 0.15). This gives the title compound as white crystals, mp 122-123 ° C.

Example 3 [Process b]

N- (l-pyrazolyl-methyl) -N- (4,6-dimethoxypyrimidin-5-yl) chloroacetamide

Prepare 347 g of N- (4,6-dimethoxypyrimidin-5-yl) chloroacetamide, 60 g of benzyltriethylammonium chloride, 3 liters of methylene chloride and 252 g of 1-pyrazolylmethyl chloride in a sulfonating flask. and 750 ml of a 30% w / w aqueous sodium hydroxide solution are added rapidly while cooling in an ice bath, and the temperature of the reaction mixture rises from 13 ° C to 25 ° C. Continuing the ice bath cooling, the reaction mixture was stirred until the temperature reached 23 ° C. At this time, the ice bath was removed and the reaction mixture was stirred for a further 2 hours, then diluted with 1.5 L of water and stirred. The organic layer was separated, dried over anhydrous sodium sulfate and filtered through a 6 cm silica pad. The silica layer was washed with 10 L of diethyl ether. The reaction mixture was concentrated to 1.5 L, the precipitate was filtered off, washed with pentane and dried in vacuo at 50 ° C. The title compound is obtained, m.p. 117-119 ° C.

Example 4

N- [1-Methyl-2- (ethoxyimino) ethyl] -N- (4,6-dimethoxypyrimidin-5-yl) chloroacetamide (Compound 64 of Table I)

12.7 g of N- [1-methyl-2- (ethoxyimino) ethyl] -4,6-dimethoxy- ² -pyrimidin-5-amine and 150 ml of dry methylene chloride are prepared in a sulfonation flask and 25 ml of dry methylene chloride are added. 6.2 g of chloroacetyl chloride were added dropwise while the reaction temperature was raised from 22 ° C to 28 ° C. The reaction mixture was then refluxed for 2 hours, cooled and 10% aqueous sodium hydroxide was added. The organic layer was separated, dried over sodium sulfate and evaporated.

The oily residue was chromatographed on silica gel with diethyl ether-hexane (1: 3) followed by diethyl ether-hexane (1: 1) to give the oily product, m.p. 82-84 ° C, which crystallized.

1-4. but using the corresponding compounds of formula (II) when using process (a) or using the corresponding compounds of formulas (III) and (IV) (L = Br), if

employing process b) or employing the corresponding compounds of formula V, if employing process c), affords the following compounds of formula Ib, which are prepared by the method described in Example 1b. Table illustrates. The R _f values in the table are for silica gel ⁴ 5.

Compound number rm R | ll R ' Y Table 1 Features 1 CH CH H -CH ₂ OC ₂ H ₅ R, = 0.15 ' 2 CH CH H -CH, C = C'H Mp = 122-123 ° C 3 CH CH H -CH ₂ CBr = CH ₂ Mp = 125-127 ° C 4 CH CH -N (CH,), -CH ₂ OC, H _s R, =:, 15 ^<2) 5 CH CH -N (CH,), -ch ₂ -c = ch Mp = 108-110 ° C 6 CH CH -N (CH ₂ ) ₂ -CH ₂ C (CH,) = CH, Mp = 80-81 ° C 7 C ₂ H _s C ₂ H ₅ H -C'H, C = CH M.p. = 73-75 ° C 8 C, H _S c, h ₅ H -CH ₂ -1-pyrazolyl M.p. = 75-78 ° C 9 n (CH ₂ ) ₂ CH H -CH ₂ -1-pyrazolyl Mp = 129-131 ° C 10 N (CH ₂ ) ₂ CH H -CH ₂ C = CH Mp = 146-148 ° C 11 N (CH ₂ ) ₂ CH H -CH, OCH ₂ CH = CH ₂ Mp = 77-79 ° C

(1) = diethyl ether;

(2) = diethyl ether-hexane 1: 1

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Compound number R ' R | ll R ' Y Features 12 N ³ C „H _S CH H -CH, CH = C Mp = 151-153'C 13 / ch, ^N H S ¹ * 5 CH H -CH ₂ -1-pyrazolyl Mp = J91-193 ° C 14 och. CH H -CH, CH = C Mp = 104-105 ° C 15 OCH, CH H -CH ₂ -! - pyrazolyl M.p. = 101-103 ° C 16 och. CH H CH, OC, H, 17 OCH, CH cl -CH, CH = C Mp = 101-103'C 18 OCH, CH OCH, -CH, CH = C Mp = 1300-132 ° C 19 OCH, CH OCH, CH, 1-pyrazolyl Mp = 148-153'C 20 OC ₄ H ,, n CH H CH, HC = C R, = O.5 ^'21 21 OC ₄ H ₉ n CH H CH, 1-pyrazolyl M.p. = 67-69 ° C 22 OCH OCH, H CH, CI Mp = 140-142 ° C 23 OCH OCH, H CH, CH, C1 Mp = 112-114 ° C 24 OCH OCH, H -CHjCH Br Mp = 118-120'C 25 OCH OCH, H -CH.CHsCH, Mp = 85-87'C 26 OCH OCH, H -CH, -C (CH,) = CH, Mp = 100-102'C 27 OCH OCH, H -CH, -OC1 = CH, M.p. = 78-80 ° C 28 OCH, OCH, H -CH, CBr = CH, Mp = 88-90'C 29 OCH OCH, H -CH, C == CH Mp = 121-123'C 30 OCH OCH, H -CH, C == C CH, C1 Mp = 103-105 ° C 31 OC., OCH, H -CH, - (2,2-dichloro-cyclopropyl) M.p. = 85-86 ° C 32 OCH OCH, H CH, COOC, H, M.p. = 61-63 ° C 33 OCH, OCH, H -CH, CON (CH, CH = CH,), M.p. = 79-81 ° C 34 OCH, OCH, H -CH-1 pyrazolyl M.p. = 117-119 ° C 35 OCH, OCH, H CH, - (3-methyl-l-pyrazolyl) 36 OCH, OCH, H -CH, 2-thiazolyl 37 OCH, OCH, H -CH, - (4-methylthiazol-2-yl) 38 OCH, OCH, H CH, - (2-methyl-thiazol-4-yl) Mp = 103-105 ° C 39 OCH, OCH, H -CH - (? - methyl-isoxazol-5-yl) Mp = 130-132'C 41) OCH, OCH, H -CH, - (2-methyl-1,3,4-oxadiazol-5-yl) Mp = 144-147'C 41 OCH, OCH, H CH, - (3-methyl-1,2,4-oxadiazol-5-yl) Mp = 129-133'C 42 OCH, OCH, H CH, - (3-ethyl-l, 2,4-oxadiazol-5-yl) Mp = 93-95'C 43 OCH, OCH, H -CH, - (1,2,4-triazol-l-yl) Mp = 131-133'C 44 OCH, OCH, H CH, -2-tiepjl Mp = 102-104 ° C 45 OCH, OCH, H -CH, -2pyrimidinyl M.p. = 173-175 ° C 46 OCH, OCH, H -CH, - (6-methyl-pyrimidin-l-yl) 47 OCH, OCH, H -CH ₂ OCH, M.p. = 89-91 ° C 48 OCH, OCH, H -CH ₂ OC ₂ H, M.p. = 73-75 ° C 49 OCH, OCH, H -CH ₂ OC, H ₇ -n 50 OCH, OCH, H -CH, OC, H ₇ -i Mp = 74-76'C 51 OCH, OCH, H -CH, OC ₄ H ₉ -n M.p. = 53-55 ° C 52 OCH, OCH, H -CH, O (CH,), OCH M.p. = 80-83 ° C 53 OCH, OCH, H -CH, OCH, CH = CH, Mp = 83-85'C 54 OCH, OCH, H -CH, OCH ₂ C = CH Mp = 122-124'C 55 OCH, OCH, H -CH, CH.OCH, M.p. = 97-81 ° C 56 OCH, OCH, H -CH, CH, OC, H, Mp = 74-76'C 57 OCH OCH, H -CH (CH,) CH ₂ OCH, 58 OCH OCH, H -CH ₂ CH = NOCH, Mp = 83-85'C 59 OCH, OCH, H CH, C (CH,) = NOCH, Mp = 103-105 ° C 60 OCH, OCH, H CH, C (CH,) = NOC H, M.p. = 82-84 ° C 61 OCH, OCH, H -CH ₂ CH = NOC, H, Mp = 90-92'C 62 OCH, OCH, H -CH (CH) CH = NOC, H ₅ Mp = 82-84'C 63 OCH, OCH, H -CH, CH = C = CH, 64 OCH, OCH, CH CH, 1-pyrazolyl Mp = 136-138 ° C 65 OCH, OCH, CH -CH, CH = C Mp = 103-106'C 66 oc _? h ₅ OC, H, H -CH, CSCH Mp = 75-77'C

(2) = diethyl ether-hexane 1: 1

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Compound number R R ' R ' Y Features 67 OC, H _S OC, H, H -CH, -1-pyrazolyl Mp = 102-104'C 68 OC ₂ H, OC, H, H -CH ₂ - (3-methyl-1,2,4-oxadiazol-5-yl) M.p. = 100-101 ° C 69 OC, H ₇ OC, H ₇ i H -CH3-1 pyrazolyl M.p. = 89-91 ° C 70 OCjH ₇ n OC, H ₇ n H -CH ₂ - '-pyrazolyl M.p. = 82-83 ° C 71 OC ₄ H ₉ n OC ₄ H ₉ n H -CH.CsCH R _f = 0.45 ¹²¹ 72 OC ₄ H ₉ n OC ₄ H ₉ n H -CH ₂ -1-pyrazolyl Mp = 51-52'C 73 N (CH,), OCH, H -CH, CH = C Mp = 112-114'C 74 N (CH ₂ ) ₂ OCH, H -CH, OCH, CH = CH, M.p. = 86-88 ° C 75 N (CH ₂ ) ₂ OCH, H -CH, pyrazolyl -'- M.p. = 89-91 ° C 76 N) CH,) ₂ OCH, H -CH, - (3-methyl-1,2,4-oxadiazol-5-yl) Mp = 139-141'C 77 N (C, H _s ), OCH, H -CH, - '-pyrazolyl Oil, R, = 0.2 < 78 N (C, H _S ), OC, H _S H -CH, - '-pyrazolyl Oil, _Rf = 0.3 ' 79 N (CH 3) C ₄ H ₉ n OCH, H -CH.C = CH R t = 0.2 ^'21 80 N (CH 3) C ₄ H ₉ n OCH, H -CH, -1-pyrazolyl M.p. = 80-82 ° C 81 cl OCH, H -CH, -C = CH Mp = 89-91'C 82 cl OCH, H CH, 1-pyrazolyl M.p. = 125-128 ° C 83 cl OCH, H -CH, 2-pyrimidinyl M.p. = 117-119 ° C 84 cl OCH, H -CH, CH (CH,) = NOCH, Mp = 83-86'C 85 cl OC ₄ H ₉ n H -CH, CH = C R f = 0.32 ^{1 (2)} 86 cl OC ₄ H ₉ n H CH, 1-pyrazolyl Mp = 73-76'C 87 cl OC ₄ H ₉ n H -CH, C) CH, CH = CH, R _f = ^0.15-13) 88 OCH, CH H -CH, CH = C M.p. = 87-89'C 89 OCH SCH, H CH, 1-pyrazolyl M.p. = 127-130'C 90 OCH, SCH, H CH, OC, H, Mp = 83-85'C 91 OCH, SCH, H -CH, OCH, CH = CH, M.p. = 87-89'C 92 SCH, SCH, H -CH, CH = C Mp = 138-141'C 93 SCH, SCH, H CH, 1-pyrazolyl Mp = 172-174'C 94 SCH, SCH, H -CH, -2pyrimidinyl Mp = 160-162'C 95 SCH, SCH, H CH, OC, H, Mp = 122-123'C 96 SCH, CH H -CH, OC, H _S 97 SCH, N (CH,), H CH, 1-pyrazolyl 98 OCH, H H -CH, CH = C Mp = 94-96'C 99 N (CH ₂ ) ₂ N (CH,), H CH, 1-pyrazolyl 100 N (CH ₂ ) ₂ N (CH ₂ ) ₂ H -CH, CH = C Mp = 80-82'C

(1) diethyl ether (2) diethyl ether-hexane 1: 1 (3) diethyl ether-hexane 1: 3

Experimental results

Experiment 1: Pre-emergence weed control by seeding seed pots with a mixture of peat nutrient and sand. The free surface of the mixture of peat nutrient and heat is sprayed with the test fluid of a test compound (e.g., prepared as in Example B). Seeds of Lepidium sativum, Agrostis alba, Avena sativa and Lolium perenne were seeded into each pot. After sowing, Avena sativa and Lolium perennial seeds are covered with a thin layer (about 0.5 cm) of a mixture of peat nutrient and sand. The pots are kept at room temperature for 14 days with 14-17 hours of daylight (daylight or equivalent illumination).

The herbicidal activity of the special herbicides was determined after a 21-day period. The finding involves a visual evaluation of the degree and quality of damage to the plants of the various seeds. θ®

The compounds of the formula I according to Table I were applied as above at a dose rate of 1.4 to 5.6 kg of active ingredient / hectare (0.140.83%) and the herbicidal activity, i.e. significant damage to the experimental plants was determined.

Experiment 2: Weed control with post-emergence treatment

The procedure used in Experiment 1 is followed, except that the test compounds (herbicides) are applied when the plants already have 2-4 leaves, stepwise planting of the seeds of the plants so that the plants have 2-4 leaves at about the same time. reach out.

The compounds of Table I are now used in the same manner at doses of 1.4 to 5.6 kg of active ingredient / hectare (0.140.831%). Herbicidal activity is determined 21 days after treatment with the test compounds and includes evaluation similar to that described in Experiment 1. The herbicidal activity of the compounds was established.

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Experiment 3

The following "Table A" relates to further evaluation of the compounds of the invention in the following experimental procedure.

The pre-emergence herbicidal activity is determined by seeding 30 to 40 cm seedlings filled with a mixture of peat nutrient and sand at a height of 6 cm. The free surface of the peat nutrient-sand mixture is sprayed with an experimental liquid (e.g., formulation B) containing a specific concentration (0.17% and 0.83%) of a compound of formula (I). The spray liquid volume corresponds to 600 liters of aqueous test fluid / hectare. Perform the same experiment with different concentrations of test fluids, choosing the concentrations. to obtain the application rates shown in the following table. Six seeds are then seeded into each bowl. The number of seeds of each plant variety sown depends on the germination capacity of the seed and the original size of the plants that emerge from each seed. After seeding, the treated surface is covered with a mixture of peat nutrient and sand to a thickness of about 0.5 cm.

The thus prepared seedlings were kept for 28 days at 20-24 ° C under illumination of 14-17 hours daily.

The post-emergence effect is similarly determined, except that the experimental herbicide is applied when the plants already have 2-4 leaves.

The herbicidal activity of each herbicide is determined 28 days after treatment with the test compound. The finding shall include a visual assessment of the degree and quality of the damage to the plants from the various seeds.

The table

The treated plant

35.sz. Compound Standard ** Growth Growth Growth Growth

before after before after kg / ha 1 5 1 5 5 5 Amaro. retrofl. 90 100 100 80 90 60 Capsellab.p. 90 90 90 30 80 90 Chenop. alb. 90 90 100 0 60 20 Galium aparine 90 90 90 10 30 60 Senecio vulg. 90 100 100 10 90 100 Stellaria media 90 90 30 0 30 10 alfalfa 90 90 90 50 90 60 Puppet 60 80 80 0 0 40 Carrot 90 100 90 0 30 30 Cotton 0 80 90 0 0 40 Flax 10 10 100 10 10 70 Potato 0 0 20 0 0 20 Soy-bean 30 90 80 0 0 20 Sugar beet 0 20 20 0 0 0 Rape 0 10 50 0 0 30

kg / ha 35.sz. compound Standard** outgrowth before outgrowth outgrowth before outgrowth after 1 5 1 5 5 5 Sunflower 0 10 60 30 0 60 Agropyron repens 90 90 50 90 100 0 Agrostis alba 100 100 - 90 100 - Alopec. myös. 90 90 90 20 50 40 Aperasp. venti 100 100 100 100 100 90 Avena fatua 80 90 90 10 40 60 Echinochloac.g. 90 100 90 90 90 90 Grain 90 100 80 0 10 50 Wheat 100 100 70 20 100 0

⁵ * 2-Chloro-N- (2-ethyl-6-methyl-phenyl) -N- (2-methoxy-1-methylethyl) -acetamide (known)

- not tested

Experiment 4: Durability study

The durability of the compounds of formula (I) was investigated in the field, where the seeds were sown 21 days after the application of the test compound (application rate of 1 kg / ha).

Visual evaluation of the degree and quality of herbicidal activity was performed 28 days after treatment with the test compound (0.11%).

The compounds have sufficient durability, as illustrated in Table B, which is shown in Table 35. Comparison of 2-chloro-N- (2-ethyl-6-methylphenyl) -N- (2-methoxy-1-methylethyl) acetamide as a standard compound.

Table B

Damage, %

Experimental Plants Compound 35 Standard

Cereal (corn) 0 0 Agrostis 85 90 Alopecurus 85 80 Setaria 90 90 Poaannua 85 90 Echinochloa crus galli 90 90

Experiment 5: Field Performance The potency of the compounds of Formula I was investigated on the field, in which weed and crop species were rowed. Treatment was carried out immediately thereafter (pre-emergence effect) or at 2-4 leaf stage of emerged plants (early pre-emergence effect). The application rates were 0.5-1.5 kg active ingredient / hectare (0.07-0.2% w / v), which were sprayed at a volume of 750 liters / hectare. The degree and quality of the effect was visually evaluated 28-42 days after treatment. The compound showed good herbicidal activity and good crop tolerance as shown in Tables C and D. The test compound was Compound 35, the standard being 2-chloro-N- (2-ethyl-6-methylphenyl) -N- (2-methoxy-1-methylethyl) acetamide.

-815

190 852

Table C

The effect of pre-outgrowth treatment

Experimental varieties of plants No. 35 compound 0.5 kg / ha 1.5 kg / ha Standard 0.5 kg / ha 1.5 kg / ha Damage ί% Grain 0 0 0 10 Wheat 0 0 0 0 Sugar beet 0 0 10th 0 Soy-bean 0 0 0 0 Potato 0 0 0 0 Rape 0 0 0 0 Avena fatua 20 40 0 0 Poaannua 0 80 0 70 Alopecurus myosuroides 20 90 10 30 Echinochloa crus-galli 10 85 40 98 Galium aparine 0 50 0 0 Amaranthus retroflexus 20 30 0 50

Table D

The effect of early treatment after outgrowth

No. 35 Compound Standard

Experimental 0.5 kg / ha 1.5 kg / ha 0.5 kg / ha 1.5 kg / ha varieties of plants % Damage Grain 0 20 0 0 Wheat 10 40 0 0 Sugar beet 0 5 0 0 Soy-bean 0 40 0 5 Potato 0 10 0 0 Rape 0 10 0 0 Avena fatua 10 10 10 0 Poa annua Alopecurus 80 90 0 0 myosuroides Echinochloa 20 90 0 10 crus-galli 85 95 0 70 Galium aparine Amaranthus 90 100 10 40 retroflexus 30 60 0 0

Pre-emergence treatment with 0.1% agent at a dose of 1 kg / ha after 28 days provided the following results.

Meto-

Active substance 9 number 35 38 39 58 79 85 ( laklór known) Plant Abutilontheoph. nt 70 20 0 70 30 80 0 Amaranthus retrofl. 100 90 100 90 90 100 100 100 Capsellab.p. 90 90 90 70 70 70 70 80 Cassía obtus. nt 60 50 10 10 20 10 10 Chenopodium album. 90 90 100 90 90 100 70 0 Daturastram. nt 90 20 100 90 60 50 50

agent number 9 35 38 39 58 79 85 Meto- laklór (known) Galium aparine 90 90 50 80 30 40 60 40 Ipomoea purp. nt 70 20 10 30 40 40 30 Portulacaol. nt 100 100 100 30 100 90 50 Senecio vulg. 90 90 90 90 90 100 90 60 Sidaspin. nt 90 60 70 30 10 10 0 Solanum n. nt 70 90 50 50 50 90 60 Stellaria m. 90 90 90 90 70 80 60 30 Agropvron rep. 100 100 90 80 100 100 90 90 Alopecurus myos. 90 100 20 80 90 90 90 10 Aperas.-Sun. 100 100 100 100 100 100 100 100 Avena fatua 80 90 30 70 90 60 80 10 Bromus tect. nt 100 90 100 100 100 100 80 Digitariasang. nt 100 90 90 100 100 100 100 Echinochloa c.-g. 90 90 90 90 90 90 80 90 Eleuisine ind. nt 100 100 100 100 100 100 100 Lolium too. nt 100 100 100 100 100 100 100 Poa annua nt 100 100 100 100 100 100 100 Setaria fab. nt 100 90 100 100 100 100 100 Sorghum halep. nt 100 90 90 100 100 90 10

nt = not tested netolachlor = 2-chloro-N- (2-ethyl-6-methylphenyl) -N- (2-methoxymethyl-ethyl) -acetamide (U.S. Patent No. 2,320,340).

Claims (2)

CLAIMS 1. An herbicide comprising 0.05-801% of the pyrimidine derivative of formula (I) as an active ingredient, wherein Y is pyrazol-1-ylmethyl, (C 1 -C 5) alkoxy (C 1 -C 5) alkyl, (C 3 -C 5) alkenyloxy) (C 1 -C 5) alkyl, (4-methylthiazol-2-yl). ) -methyl or (2-methylthiazol-4-yl) methyl, R ₇ and R ₈ are each independently a solid or liquid carrier or diluent for C 1-4 alkyl, C 14 alkoxy or di (C 1-4 alkyl) amino, preferably natural or artificial mineral ground, aliphatic, aromatic or cyclic hydrocarbon, water, [mineral oil fraction and surfactant] additive, preferably at least one ionic or non-ionic dispersant, emulsifier, wetting agent. 2. A process for the preparation of pyrimidine derivatives of formula Ib in the formula R ₉ and R ₁₁ are independently C 1-4 alkyl, C 14 alkoxy, C 1-4 alkylthio, di (C 1-4 alkyl) amino or N (C 1-4 alkyl) -N-. phenylamino, hydrogen or halogen; R _{n is} hydrogen, halo, C 1-4 alkyl, C 1-4 alkoxy, or di (C 1-4 alkyl) amino; Y _{is C} 1 -C 5 monohaloalkyl, C 3 -C 5 alkenyl or alkynyl optionally monosubstituted with halogen, and C 1 -C 4 alkoxy optionally; -917 (C 1 -C 4 alkoxy) (C 1 -C 3 alkyl) mono-substituted (190,852), [halo (C 3 -C 6 cycloalkyl)] - (C 1 -C 4 alkyl), (C 3 -C 5 alkynyl). Oxy (C 1 -C 3 alkyl) or (C 3 -C 5 alkynyloxy) (C 1 -C 3 alkyl); -CH3-COY wherein Y is C1-C4 alkoxy or di (C3-C6 alkenyl) amino; R _{2 is} -A ₂ , wherein R _{2 is} -CH ₂ -. A, 1-diazolyl or 1-triazolyl, or a five membered heterocyclic group bonded to the -CH ₂ - group containing a carbon atom and containing a sulfur atom or a nitrogen atom and an oxygen or sulfur atom, or a 2-pyrimidinyl group, and heterocyclic ring optionally monosubstituted with C 1 -C 4 alkyl, characterized in that a) in a compound of formula II wherein R ₉ , R ₉ '. R _n and Y _are as defined herein - the hydroxy group of the N-hydroxyacetyl group is replaced by a chlorine atom in a known manner, or b) reacting a compound of formula (III) - wherein R _9, R _l, and the meanings of R _n areas - a compound of formula (IV) wherein Y, defined and L is a leaving stated above, preferably a halogen atom -Nalkilezünk; obsession c) N-acylating a compound of formula V wherein R ₉ , R _{1 (1} , R ₁ , and Y "are as defined) with chloroacetyl chloride.