HU206688B - Herbicide and growth-controlling compositions containing substituted pyrimidine derivatives and process for producing the active components - Google Patents

Abstract

Field of the Invention The present invention relates to herbicide and plant growth regulating compositions and to the preparation of new pyrimidine derivatives of the formula (I), which form an active ingredient thereof. Compounds of formula (I), which can be prepared by methods well known in the art of organic chemistry, are n or 3,4, R1 and R2 are independently halogen or C1-C4 alkyl or C1-C4 alkoxy, and Z is hydroxy or 1 C5-alkoxy. R2 EN 206 688 B Scope of description: 8 pages (including 1 sheet)

Description

The present invention relates to herbicidal and plant growth controlling compositions containing substituted pyrimidine derivatives, and to the preparation of their active compounds.

Many 2-substituted pyrimidine derivatives are known in the art as plant growth regulators or herbicides.

For example, German Patent No. 109,170 discloses 2-alkyl (or alkenyl-, aralkyl- or aryloxy) -pyrimidine derivatives which have valuable plant growth regulating activity and are capable of regulating metabolic and growth processes such as root formation and to promote growth, assist in fruit ripening, or provide dwarf growth for certain plant development parameters.

Recently, for example, various 2-aryloxy or 2- (arylthio) pyrimidine derivatives have been disclosed in European Patent Specifications 223 406 and 249 708 and Japanese Patent Application Nos. 63258,462 and 63-258,463 which all have herbicidal properties.

We have found that pyrimidine derivatives which exhibit a particularly valuable herbicidal activity

They carry a 2-substituted cycloalkoxy group, i.e. they are very spatially different in structure from the alkyl and aryloxy or thio-pyrimidine derivatives known hitherto.

The present invention therefore relates, on the one hand, to a novel herbicidal and plant growth regulating composition comprising as active ingredient a compound of formula (I) or an equivalent amount of an inorganic or organic cation salt thereof. In the formula (I), n is 3, 4 or 5,

R ¹ and R ² each independently represent halogen or C 1-4 alkyl or C 1-4 alkoxy, and

Z is hydroxy or C 1-5 alkoxy.

The alkyl group or alkyl moiety preferably contains from 1 to 4 carbon atoms, particularly preferably 1 or 2 carbon atoms.

As the salts of the carboxylic acids of the formula I, salts with inorganic cations such as alkali metals, alkaline earth metals such as sodium, potassium, calcium or magnesium, transition metals such as copper, salts formed with cations.

The cycloalkyl ring of formula (I) may thus be a cyclopentyl, cyclohexyl or cycloheptyl ring, particularly preferably a cyclopentyl or cyclohexyl ring.

Preferably R ¹ and R ² each independently represents a chlorine atom or a methyl or methoxy group.

A preferred example of Z is C 1-4 alkoxy.

It will be appreciated by those skilled in the art that the compounds of the present invention may exist in various stereoisomeric forms. These compounds, as denoted by * and ** in formula (Ia), have two chiral centers, so that there are two types of diastereoisomers, each of which is a mixture of two enantiomers. It will be appreciated by those skilled in the art that each of the isomeric forms of the compounds of formula (I) and mixtures thereof in any proportion are included within the scope of the present invention. It will also be understood by one skilled in the art that some isomers may have greater activity than another isomer or mixture of isomers of the same compound.

The invention further relates to a process for the preparation of compounds of formula (I). According to the present invention, a compound of formula (II) wherein R ¹ and R ² are as defined for formula (I) and L is a leaving group is prepared with a compound of formula (III) wherein n is The compound of formula I, while Z 'is a C 1 -C 5 alkyl group, is optionally hydrolyzed to form a compound of formula I, and optionally the free carboxylic acid of formula I is converted into a salt or free salt of such a salt. liberating acid or converting such a salt into another salt,

The leaving group may be any group which, under the given reaction conditions, will be cleaved from the starting material and thereby accelerate the reaction at the desired site.

For the compounds of formula II, the leaving group L is suitably a halogen atom such as bromine, chlorine or iodine or, preferably, an alkanesulfonyl group, preferably methanesulfonyl group.

Preferably, the reaction of the compounds of the formulas II and III is carried out under basic conditions. The basic conditions may conveniently be provided, for example, by an alkali metal hydride such as sodium or potassium hydride, an alkaline earth metal hydride such as calcium hydride, an alkali metal carbonate or bicarbonate such as sodium or potassium carbonate carbonate, an alkali metal alcoholate such as potassium tert-butylate or a tertiary amine such as triethylamine, pyridine or 1,8-diazabicyclo (5.4.0) undec-7-ene.

The reaction is conveniently carried out in an inert organic solvent such as a hydrocarbon such as benzene or toluene, a chlorinated hydrocarbon such as dichloromethane or chloroform, an alcohol such as methanol or ethanol, an ether such as diethyl ether, tetrahydrofuran or 1,4- dioxane, a ketone such as acetone or methyl ethyl ketone, an ester such as ethyl acetate, an aprotic polar solvent such as dimethylformamide, dimethylacetamide or dimethylsulfoxide, a nitrile such as acetonitrile or water. solvent, depending on the quality of the reagent providing the basic conditions.

The reaction is carried out over a wide temperature range

The reaction may be carried out, for example, at room temperature, that is, between about 20 ° C and the boiling point of the reaction mixture.

The amount of the starting compounds of formula (III) and (III) is conveniently selected from 0.1 mol to 10 mol of compound (Π) per mole of compound (III). In general, however, it is preferable to use substantially equimolar amounts of the compounds of formula (Π) and (III).

The diastereoisomers and enantiomers of the compounds of formula (I) may, of course, be prepared from the appropriate stereospecific starting materials by the process of the present invention, finally by appropriate separation, such as chromatography, or, if a mixture of optical isomers is formed.

Compounds of formula (I) wherein Z is alkoxy may be hydrolyzed to the corresponding acids of formula (I) as is well known in the art.

The preparation of salts and the release of acids from the salts can be carried out in a manner known per se.

The compounds of formula (I) obtained by the process of the invention may be isolated or, if desired, purified by methods well known in the art.

The starting pyrimidine derivatives of formula (Π) can be prepared in a known manner, for example, as described in Volume 16, "The Pyrimidines" of the 1962 series "Heterocyclic Compounds" edited by Brown, D.J., Interscience.

The starting compounds of formula (III) are known compounds or may be prepared in a known manner, for example by reduction of a suitable cycloalkanone-2-carboxylate with suitable reduction. conditions such as sodium borohydride in an inert solvent.

Formulations containing up to 95% by weight of the compounds of formula I can be used as herbicidal compositions against unwanted weeds, both pre- and post-emergence. The compositions of the present invention thus contain, in addition to the active ingredient, carriers and / or other excipients commonly used in compositions of this type. These compositions may be prepared in known manner.

The compositions of the invention preferably contain at least two types of excipients, at least one of which is a surfactant.

The compositions of the invention may be applied in the usual manner to the environment of the plant to be destroyed or to the vegetation itself or to the soil in which it grows. As mentioned, the treatment may be in a preemergent or postemergent manner. The amount of active ingredient is generally 0.01 kg to 10 kg, preferably 0.01 kg to 4 kg per hectare.

The carrier of the compositions of the present invention may be any material which enables the active ingredient to be formulated or applied to a plant, plant seed desirable soil, and to facilitate storage, handling or transport of the active ingredient. Such a carrier may be solid or liquid, including materials which are normally gaseous but can be compressed into liquids. Any known carrier commonly used in herbicidal compositions may be used. Preferably, the compositions of the invention contain from 0.5 to 95% by weight of the active ingredient.

Suitable solid carriers include natural and synthetic materials and silicates, such as natural silicates, such as diatomaceous earth; magnesium silicates, such as talc; magnesium aluminum silicates, such as attapulgites and vermiculites; aluminum silicates, such as kaolinites, montmorillonites and mica; calcium carbonate; calcium sulfate; ammonium sulphate; synthetic hydrated silicas and synthetic calcium or aluminum silicates; elements such as carbon and sulfur; natural and synthetic resins such as coumarone resins, polyvinyl chloride and styrene polymers and copolymers; solid polychlorophenols; bitumen; waxes; and solid fertilizers such as superphosphates.

Suitable liquid carriers include water; alcohols such as isopropanol and glycols; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethers; aromatic or araliphatic hydrocarbons such as benzene, toluene and xylene; kerosene fractions such as kerosene and light mineral oils; chlorinated hydrocarbons such as carbon tetrachloride, perchlorethylene and trichlorethylene. Mixtures of different liquids are often useful.

Agricultural formulations are often formulated and transported in a concentrated form which is then properly diluted by the user before use. The presence of small amounts of surfactant aids the dilution process. Therefore, at least one of the excipients is preferably a surfactant for the compositions of the invention. For example, the composition of the invention may contain at least two types of excipients, at least one of which is a surfactant.

Suitable surfactants are emulsifiers, dispersants or wetting agents which may be nonionic or ionic. Suitable surfactants include, for example, sodium or calcium salts of polyacrylic acids and lignin sulfonic acids; condensation products of ethylene oxide and / or propylene oxide with fatty acids or aliphatic amines or amides containing at least 12 carbon atoms; esters of fatty acids with glycerol, sorbitol, sucrose or pentaerythritol; condensates thereof with ethylene oxide and / or propylene oxide; fatty alcohols or alkyl phenols, e.g.

For example, condensation products of 4-octylphenol or 4-octylcresol with ethylene oxide and / or propylene oxide; sulfates or sulfonates of these condensation products; alkali or alkaline earth metal salts of sulfuric or sulfonic acid esters containing at least 10 carbon atoms, preferably sodium salts such as sodium lauryl sulfate, sodium sec-alkyl sulfates, sodium sulfonates of sulfonated red oil and e.g. sodium salts of benzenesulfonate; and polymers of ethylene oxide and copolymers of ethylene oxide and 1 propylene oxide.

The herbicidal compositions of the present invention may contain additional biologically active components, such as herbicidal, insecticidal or fungicidal compounds. 1

The following examples are intended to illustrate the invention. The structure of the compounds prepared in the Examples was confirmed by mass spectrometry and NMR. The resulting compounds are in the diastereomeric form and thus the cis and trans expresses the spatial configuration of the diastereomers produced.

Example 1

Ethyl Cis-2- (4,6-Dimethoxy-pyrimidin-2-yloxy) -cyclohexanecarboxylate 2

a) To a solution of ethyl cyclohexanone-2-carboxylic acid ethyl ester (85.0 g, 0.5 mol) in ethanol (200 ml) at 0 ° C was added small amounts of sodium borohydride (13.2 g, 0.35 mol) in ethanol (80 ml). while maintaining the temperature of the reaction mixture at 0 ° C during the addition. After the addition was complete, the reaction mixture was stirred at the same temperature for 2 hours, then acidified with 50% aqueous sulfuric acid and filtered. The filtrate was concentrated in vacuo and the residue taken up in diethyl ether 3. The resulting solution was washed with aqueous sodium bicarbonate solution, dried over anhydrous magnesium sulfate and evaporated in vacuo. The residue was purified by chromatography on silica gel eluting with hexane: ethyl acetate (3: 1, 4: 4) and hexane: ethyl acetate (2); Using a 1 volume mixture. 21.5 g of cis and 10.0 g of ethyl ethyl trans-2-hydroxycyclohexanecarboxylate are obtained.

b) was added dropwise to a stirred mixture of 0.48 g of above 60% w ásványola- ^z oracle sodium hydride dispersion in 20 mL of anhydrous dimethylformamide cis-hydroxy-ester obtained in step a) (1.72 g 0, A solution of 1 mol) in anhydrous dimethylformamide (10 ml) was added, followed by stirring for 30 minutes, 4,6-dimethoxy-2- (methanesulfonyl) pyrimidine (2.18 g, 0.01 mol). The resulting mixture was stirred at 90 ° C for 16 hours and then concentrated in vacuo. The residue was diluted with water and extracted with diethyl ether. The extract was dried over anhydrous magnesium sulfate and evaporated. The crude product was purified by chromatography on silica gel (hexane: ethyl acetate = 3: 1). This gave 1.5 g (48%) of the title compound.

Analysis results:

Calculated: C, 58.0; H, 7.1; N, 9.0;

Found: C, 57.8; H, 7.2; N, 9.0.

Example 2

Cis-2- (4,6-dimethoxy-pyrimidin-2-yl) cyclohexanecarboxylic

A solution of sodium hydroxide (0.17 g) in water (20 ml) was added to a stirred solution of ethyl ester (1.3 g) in methanol (20 ml) and the resulting mixture was stirred at room temperature overnight and concentrated in vacuo. The residue was diluted to 100 ml and the aqueous solution was washed twice with diethyl ether and then acidified with dilute hydrochloric acid. The acidic aqueous mixture was dried over anhydrous magnesium sulfate and evaporated in vacuo. Trituration of the residue with hexane gave the crude product as a white precipitate, which was recrystallized from a mixture of water and methanol. 0.6 g (51%) of the title compound is obtained, m.p. 151-152 ° C.

Analysis results:

Calculated: C, 55.3; H, 6.4; N, 9.9;

Found: C, 55.3; H, 6.5; N, 10.1.

3-16. examples

In a similar manner to that described in Examples 1 and 2, the compounds listed in Table 1 can be prepared, the analytical results and, if solid, the melting points are also given. In the table, compounds are identified by reference to formula (Ib).

/. spreadsheet

The serial number of the example R ¹ R ² n Z isomer form melting point (° C) Analysis Results (%) C H N calculated Found 3 and ₃ OCH ₃ 3 oc ₂ h ₅ mix oil 56.8 6.8 9.5 56.7 6.5 9.7 4 and ₃ and ₃ 3 oc ₂ h ₅ trans 30-32 56.8 6.8 9.5 56.2 6.7 9.8

HU 206 688 Β

The serial number of the example R ¹ R ² n Z isomer form melting point (° C) Analysis Results (%) C H N calculated Found 5 and ₃ and ₃ 3 OC ₂ H ₅ cis oil 56.8 6.8 9.5 56.4 6.7 9.7 g and ₃ and ₃ 4 oc ₂ h ₅ trans oil 58.1 7.1 9.0 58.4 7.2 9.4 7 and ₃ and ₃ 5 and ₃ trans oil 58.0 7.1 9.0 58.2 7.2 9.5 8 and ₃ and ₃ 5 and ₃ cis oil 58.0 7.1 9.0 9 and ₃ and ₃ 4 and ₃ cis 72.5 56.8 6.8 9.5 56.6 6.7 9.8 10 and ₃ and ₃ 4 and ₃ trans oil 56.8 6.8 9.5 56.1 6.7 9.6 11 and ₃ and ₃ 4 OH trans 168.0 55.3 6.4 9.9 55.9 6.3 9.9 12 ch ₃ ch ₃ 4 and ₃ cis oil 63.6 7.6 10.6 63.4 7.7 10.1 13 ch ₃ ch ₃ 4 and ₃ trans oil 63.6 7.6 10.6 63.3 7.5 10.8 14 and ₃ and ₃ 3 and ₃ trans oil 55.3 6.4 9.9 55.2 6.4 10.4 15 and ₃ and ₃ 3 and ₃ cis oil 55.3 6.4 9.9 56.1 6.4 9.8 16 and ₃ and ₃ 3 OH trans 113.7 53.7 6.0 10.4 53.8 5.9 10.8 17 and ₃ and ₃ 5 OH trans 103.9 56.8 6.8 9.5 57.9 6.3 9.3 18 cl and ₃ 4 OC ₂ H ₅ cis oil 53.4 6.0 8.9 55.0 6.2 8.4

Example 19

Trans-2- (4,6-dimethoxypyrimidine-24-oxy) -N-benzenesulfonyl) -cyclohexanecarboxamide A solution of 0.57 g of 1,1-carbonyldiimidazole in 10 ml of anhydrous tetrahydrofuran is added dropwise with stirring under a nitrogen atmosphere. A solution of trans-2- (4,6-dimethoxypyrimidin-2-yloxy) -cyclohexanecarboxylic acid (1.0 g) prepared in Example 11 in 50 ml of anhydrous tetrahydrofuran was added and the resulting mixture was stirred at room temperature for 30 minutes. stir, reflux for 30 minutes, and finally cool to room temperature. Then, 0.56 g of benzenesulfonamide and a solution of 0.54 g of 1,8-diazabicyclo (5.4.0) undec-7-ene in 5 ml of anhydrous tetrahydrofuran are added dropwise.

After stirring at room temperature for 24 hours, the reaction mixture was refluxed for 6 hours and then poured into 80 ml of 1N aqueous hydrochloric acid. 60

The resulting aqueous mixture was extracted with diethyl ether (3 x 100 mL), and the combined extracts were dried over anhydrous magnesium sulfate and evaporated. The residue was purified by chromatography on silica gel using a 2: 1 by volume mixture of dichloromethane and ethyl acetate as eluent. 100 mg of the title compound are obtained, m.p.

Analysis results (%):

Calculated: C, 54.1; H, 5.5; N, 10.0;

Found: C, 53.8; H, 6.0; N, 10.3.

Example 20

Herbicidal activity

For the evaluation of herbicidal activity, formulations containing the compounds of the invention are tested on the following representative plants: maize (Zea mays, abbreviated as Mz); rice (Oryza sativa, abbreviated as R), cocksfoot (Echinochloa

HU 206 688 Β crus-galli, abbreviated as BG); oats (Avena sativa, abbreviation:

0); flax (Linum isitatissimum, abbreviated as L); mustard (Sinapis alba, abbreviated as M); beet (Beta vulgar, abbreviated SB) and soybean (Glycine max, abbreviated S).

There are two types of experiments, namely preemergent and 5 postemergent. In preemergent experiments, a liquid composition comprising a compound of the present invention is sprayed onto soil in which seeds of the plant species listed above have been sown. In the post-emergence experiments, there are two types of experiments, namely soaking and foliar spraying. In soil irrigation experiments, soils containing seedlings of the plants listed above are soaked in a liquid formulation containing one of the compounds of the present invention, while in foliar spray experiments, growing seedlings are sprayed with the same formulation.

The soil used in the experiments is clayey soil for horticultural purposes.

The formulations used in the experiments are prepared from solutions of the compounds of the invention in alkylene phenol ethylene oxide concentrate type 0.4 (w / w) in the amount of 0.4% by weight of TRITON X-155. These acetone solutions are diluted with water and the resulting formulations are applied at a rate of application of 5 kg or 1 kg of active ingredient per 600 hectares, 600 liters per hectare in soil spraying and foliar spraying applications and 10 kg per hectare in soil irrigation experiments. and dispensed in a volume of nearly 3,000 liters.

Untreated and sown soil in pre-emergence experiments and untreated seedlings in post-emergence experiments were used as controls.

The herbicidal activity of the compositions of the present invention is determined visually 12 days after spraying the soil and foliage and 13 days after the soil is soaked and then evaluated on a scale of 0 to 9. A scale of 0 indicates the same increase as the untreated control, whereas a scale of 9 indicates extinction. On this linear scale, an increase of 1 unit corresponds to a nearly 10% increase in effect.

The results obtained are given in Table 2, in which the test compounds are identified by a number of previous examples. An asterisk in the table indicates that no results were obtained.

Table 2

Serial number of compound Soil irrigation (10 kg / ha) Dose Foliar spraying Preemergent test Mz R BG SHE L M SB s kg / ha Mz R BG 0 L M SB S Mz R BG SHE L M SB S 1 8 8 8 8 7 8 9 7 5 5 8 7 7 7 8 8 8 8 9 8 8 7 7 8 8 1 4 8 5 7 7 7 8 7 6 9 7 7 6 7 8 4 2 8 8 8 8 8 8 9 8 5  8 8 9 8 8 8 8 8 8 9 9 8 8 8 8 8 1 7 8 7 8 7 8 8 7 8 9 9 8 8 8 8 6 3 7 6 7 7 7 8 8 4 5 7 4 7 6 7 8 7 7 7 9 8 7 6 7 8 4 1 7 2 5 5 6 8 7 6 4 9 7 4 2 7 7 1 4 ₇ 7 7 7 7 8 7 6 5 7 5 8 6 7 8 8 8 8 9 9 7 8 7 7 8 1 7 2 7 4 7 8 8 8 7 9 8 5 7 7 7 7 5 7 7 ₇ 7 4 8 7 4 5 4 3 4 3 4 7 5 5 3 8 5 4 0 5 3 0 1 * * * * * & * * * * * * Φ * 6 8 8 8 8 7 9 9 8 5 7 8 8 8 7 9 9 8 8 9 9 8 9 7 8 8 1 7 8 8 8 7 8 8 8 8 9 9 8 7 7 8 8 7 7 7 8 7 7 7 8 7 5 7 6 8 7 7 8 8 7 9 9 9 8 8 7 8 8 1 6 6 6 6 6 7 7 7 8 9 9 7 7 7 8 7 8 7 7 7 7 6 6 7 6 5 6 6 8 6 7 7 8 6 7 8 8 7 7 6 8 2 1 2 5 3 5 6 4 5 4 5 7 7 6 5 5 6 0 9 7 7 7 7 7 7 8 7 5 7 7 7 7 7 7 8 7 8 9 9 8 8 7 8 8 1 6 7 5 7 6 5 7 7 7 9 8 7 7 6 8 8 10 8 8 9 9 8 8 8 8 5 8 8 9 8 8 9 8 8 9 9 9 8 9 8 8 8 1 8 8 8 8 8 8 8 8 9 9 9 8 8 8 8 8 11 9 9 9 8 8 9 9 8 5 9 9 9 9 8 9 8 8 9 9 9 9 9 8 8 8 1 8 8 9 8 8 8 8 8 9 9 9 8 9 8 8 8

HU 206688 Β

The chemical track of today Soil irrigation (10 kg / ha) Dose Foliar spraying Preemergent test Mz R BG 0 L M SB s kg / ha Mz R BG 0 L M SB s Mz R BG 0 L M SB s 12 7 7 7 6 3 6 8 3 5 6 6 7 7 0 2 3 2 7 8 9 7 2 0 5 0 1 2 6 7 5 0 2 0 0 4 7 8 6 0 0 3 0 13 7 7 8 6 0 3 7 2 5 2 6 7 4 0 4 4 0 5 $ 7 6 2 2 2 0 1 0 5 4 2 0 1 1 0 1 4 5 3 0 0 0 0 14 - 7 7 8 6 7 7 8 5 5 7 7 7 3 7 8 9 8 8 * 8 4 7 7 8 4 1 6 6 6 2 6 7 8 5 4 8 8 1 5 6 7 3 15 7 7 7 6 4 7 9 2 5 4 7 5 2 5 7 9 3 4 7 8 6 4 7 5 0 1 1 6 3 0 3 6 6 1 1 5 6 2 1 5 3 0 16 7 8 8 5 8 8 8 5 5 7 7 8 6 8 8 8 8 8 9 8 6 7 7 8 8 1 7 7 8 6 7 8 7 8 7 9 8 3 5 6 7 2 17 7 8 8 7 6 8 9 7 5 7 7 8 7 6 7 8 7 8 9 8 6 7 6 8 3 1 * * * * * * * * * * * * * * * * 18 8 8 7 8 4 7 8 8 5 5 7 7 7 7 7 8 6 8 9 9 8 8 8 8 4 1 3 6 4 6 6 6 . 8 4 4 8 9 7 7 6 8 3 19 * * * * * * * * 5 0 5 7 4 6 7 4 5 2 5 7 6 5 6 6 3 1 * * * * * * * * * * * * * * * *

PATENT CLAIMS

Claims (3)

PATENT CLAIMS CLAIMS 1. A herbicidal or plant growth regulator composition comprising up to 95% by weight as an active ingredient of a compound of formula I wherein n is 3,4 or 5, R ¹ and R ² are each independently halogen C 1-4 alkyl or C 1-4 alkoxy; and Z represents a hydroxyl or C 1 -C 5 alkoxy group or an agriculturally acceptable salt thereof, together with customary carriers and / or other excipients. Composition according to Claim 1, characterized in that it contains as an active ingredient a compound of the formula I in which R * and R ² independently represent a chlorine atom or a methyl or methoxy group. 3. A process for the preparation of compounds of formula I and salts thereof wherein n is 3,4 or 5, R ¹ and R ² independently of one another are halogen or C 1 -C 4 alkyl or C 1 -C 4 alkoxy, and Z is hydroxy or C 1 -C 5 alkoxy, characterized in that 35 a compound of formula II wherein R ¹ and R ² are as defined for formula I and L is a leaving group for a compound of formula III wherein n is as defined for formula I; While Z 'is a C 1 -C 5 alkyl group, optionally hydrolyzing a compound of formula I thus obtained and optionally converting the resulting free carboxylic acid of formula I into a salt or a salt thereof. 45 free acids are liberated or one of these salts is converted to another salt.