CS201016B2 - Herbicide - Google Patents

Description

The present invention relates to pyridine derivatives having herbicidal properties, herbicidal compositions and processes utilizing these compounds.

The invention relates to pyridine derivatives of the general formula I,

(I) wherein each of Z and Y represents a fluorine, chlorine, bromine, iodine or hydrogen atom, a trifluoromethyl group, a difluoromethyl group or a chlorodifluoromethyl group, provided that at least one of Z and Y is a halomethyl group,

R ^{@ 1} is hydrogen or C1 -C4 alkyl and

R ² represents cyano, carboxyl, carboxamido of the formula

-CNR ³ R ⁴ where R is hydrogen or C 1 -C 4 alkyl and R 4 is hydrogen, C 1 -C 4 alkyl, optionally substituted by hydroxyl or phenyl, phenyl, chlorophenyl, alkoxy or a group of the formula -Nr 5r ⁸ , where ^R is hydrogen or C 1 -C 4 alkyl and R ⁸ is hydrogen, alkyl. C 1-4 alkyl, phenyl or C 1-4 alkyl. chlorophenyl, or wherein the group -NR ^ R ^ forms rorcolMlno- Piper ^d ino- not moofolinos ^b of ^{the fastening,} or a radical of formula

wherein R ⁷ is C 1 -C 4 alkyl or phenyl, or R is alkoxycarbonyl, wherein the alkoxy moiety contains 1 to 8 carbon atoms, may be straight or branched and optionally bears one substituent selected from the group consisting of hydroxyl groups, C 1 -C 4 alkoxy and halogen atoms, or carries a substituent corresponding to the above general formula (I) in which ^R is -S-Ο- or represents: ( ¹⁶⁾ (OCH ² CH ₂ ) _n 0R ⁸ *

where

Q

R represents a (C1-C4) alkyl group and a R6 value of 1 to 5, or is a cyclohexyl-2-oxoalkyl group optionally substituted by a halogen atom or a butterfly group, an alkeuyloxycarbonyl group in which the alkenyl moiety contains 3 to 6 carbon atoms; optionally substituted with a halogen atom or a butterfly atom. or a benzyloxycarbonyl group whose phenyl moiety Re is optionally substituted by a halogen atom or a methyl group, and salts of those compounds in which R is a carboxyl group.

The compounds of the invention in which R is a carboxyl group can be prepared by conventional methods for the preparation of carboxylic acid salts. Typical salts include metal salts and ammonium salts. Metal soils formed with alkali metal cations, e.g. sodium, potassium and lithium, and salts formed with alkaline earth metal cations such as calcium, steeplechase and magnesium. The anionic salts include those formed with an ammonium cation or with a mono-, di-, tri-, or thetaester of ammonium cation, wherein the subsituents may be, for example, aliphatic groups having 1 to 6 carbon atoms, such as alkyl groups having 1 to 6 carbon atoms.

One of. groups of compounds of the invention form compounds wherein Z is trifluoromethyl. Nominal 2 group, Y is hydrogen, R₁ ethyl group and R has the above disclose a significance in this SKU ^p in the compounds ^{of R 2} may be bakes and ^d kartoxylovou group and leave Cancer ^ ^t and in.

in the form of a salt, or may be an alkoxycarbonyl skipine, for example a alkoxycarbonyl group, both of which are set. in the alkoxy moiety of 1 to 6 carbon atoms.

Another group of compounds of the invention are those in which Z. represents a trifluoromethyl group, Y a chlorine atom, R ^{1 is a} butterfly group and R ² is as defined above. In this group of compounds, R @ ² can be, for example, a carboxyl group, either free or in the form of a salt, or can be an alkenyl group, for example a cyclohexyl group enriching. C 1 -C 6 alkoxy.

• i

Another group of compounds are compounds wherein Z is dlfui ^ c ^ i ^ m ^ ^ itlh LLOV or chl2oaifl2om etýloí2l group ^γ ^ are hydrogen or chlorine ^r1 butterfly group and R is as defined above. In this group of compounds, R @ ² can be, for example, a carboxyl group, both free and in the salt form, or can be a alkoxycarbonyl group, for example an alkoxycarbonyl group containing from 1 to 6 carbon atoms in the alkoxy moiety.

Compounds of the invention, except ^for LATE ava ^h otecnéto formula I wherein ^R1 is hydrogen, voluminous asymmetric carbon atom and can therefore exist in two optically active isomeric forms. The invention encompasses both the dextrorotatory and levorotatory isomers of all such compounds of the invention, and their siamsi in all fields.

Colortative examples of the compounds of the invention are summarized in Table I below.

Table I

compound number OF Y r ’ R ⁹ physical constants (melting point - m.p. or boiling point - 1 CF3 H «» 3 OH m.p. 100 ALIGN! 2 CF ₃ H OH . OCH3 t.v. 134-138 / 6.7 Pa 3 CF _? H ^CH 3 °° 2 ^Η 5. oil 4 <* 3 H CH3 (O ^ n t.v. 155 / 6.7 'Pa 5 CF3 H CH. (^ n t.v. 167 / 6.7 Pa 6 CF3 H Tail t.v. 167 / 6.7 Pa 7 CF3 H ch3 ^^ iso t.v. 165 / 6.7 Pa 8 CF3 H CH3 ^ ₅ R, n oil 9 CF3 H CH3 ^C «3 oil OCHC-jH? 10 CF3 H CH3 CH _V ¹³ OCHCH ₂ CH (CH ₃ ) ₂ oil 11 ^CF3 H CH3 OC ^CH CHH H oil 12 CF3 H CH3 ^OC 6 ^H 13 ³ⁿ oil 13 CF3 H CH3 O-cyclohesxyL oil 14 CF3 H CH3 θ ² * ⁵ oil OCH 2 CH-C 4 H 9 oil 15 Dec CF ₃ H CH3 OCRCROC ^ oil 16 CF ₃ H CH3 °° 8 ^Η 17 ^° oil 17 CF ₃ H CH3 nhc ₃ h ₅ m.p. 96-98 18 CF3 H CH3 nh ₂ m.p. 168-170 19 Dec OF. * H CH3 NHCRCl 3 NH.CgH4.Clp m.p. 126-128 20 May cpJ H C,' m.p. 147-149 21 CF ₃ H ^CH nhch ₂ h ₂ ° h m.p. 72-74 22nd CF ₃ H ch3 NHNH.C ₆ H ₄ ClCl solid 23 CF, H CH3 N ^(CH3) 2 oil 24 ₃ ° F H CH ₃ OCRCHsCR oil 25 CF3 H CH3 ^C 6 ^H 5 oil 26 CF3 H CH3 OCg ^ .C ^ m oil 27 Mar: CF3 H ^CH 3 OCH ₂ CgH ₅ oil 28 CF3 Cl ' CH3 OH m.p. 104-107 29 CF3 CL CH ₃ ° CH3 oil 30 CF3 CL CH3 ° C 2H ₅ oil 31 CF ₃ cl CH3 aCjRn oil

compound number OF Y R ¹ R ⁹ physical constants (melting point - melting point or boiling point b.p.) 32 CF-j Cl ^CH 3 ОС, Н? 180 oil 33 CF ₃ Cl CH ₃ 0C ₄ H ₉ n oil 34 CF ₃ Cl. CH ₃ OC ^ H ^ sec oil 35 CF ₃ Cl ch ₃ OC ₄ H ₉ iso oil 36 CF ₃ Cl CH ₃ θ ^ 5 ^ 11 ⁿ oil 37 CF ₃ Cl • CH ₃ f ^H 3 OCHCH ₂ CH (CH ₃ ) ₂ oil 38 ^CF 3 Cl CH ₃ O-Cyclohexyl oil 39 CF ₃ Cl CH ₃ 2 ^H 5 oil OCH ₂ CHC ₄ H ₉ 40 CF ₃ Cl CH ₃ OCHgCHgOH oil ’· 41 CF ₃ Cl CH ₃ OCH ₂ CH ₂ OCH ₃ oil 42 ^CF 3 Cl CH, °° 8 ^Η 17 ^° oil 43 CF ₃ Cl CH ₃ N _{(CH3) 2} oil 44 CF ₃ Cl CH ₃ “V- / ⁰ m.p. 99-100 45 ^CF 3 Cl CH ₃ NHC ₆ H ₅ m.p. 135-136 46 ^CF 3 Cl CH ₃ -NHNHC ₆ H ₅ m.p. 109-1Ю 47 CF ₃ Cl CH ₃ OCH 6 CH m.p. 57.5-58.5 48 CF ₃ Cl CH ₃ OCH ₂ CH ₂ Cl m.p. 79.0-81.5 49 CF ₃ Cl CH _? OC ₆ H ₄ ClCl m.p. 63-64 50 CF ₃ Cl ^CH 3 sc ₆ H ₅ solid 51 CF ₃ Cl ^CH 3 NHCH, m.p. 148-149 52 CICFg H CH ₃ oc ₂ H ₅ oil 53 C1CF ₂ Cl CH ₃ oc ₂ H ₅ m.p. 61-62 54 CICFg Cl CH ₃ OCH ₂ CH ₂ Cl oil 55 cicf ₂ Cl CH ₃ OCH ₂ CH = CH ₂ oil 56 cicf ₂ Cl CH ₃ 0 · C ₄ H ₄ ClCl oil 57 C1CF ₂ Cl CH, NHCH, solid 58 C1CF ₂ Cl CH ₃ NHNH.C ₆ H ₄ ClCl solid 59 CF ₃ Br CH, ^0C 2 ^H 5 oil 60 CF _? Br CH, 0C ₄ H ₉ n oil 61 Cl CF ₃ CH, OC ₂ ^H 5 oil 62 Cl Whose\ CH ₃ OC ₄ H ₉ n oil 63 Cl % CH ₃ OCH ₂ CH ₂ OCH ₃ oil 64 Cl OF. CH, / “X —N o solid J J 65 Cl CF- CH, NHC ₆ H ₅ solid 66 Cl CF ₃ ^CH 3 осн ₂ с _б и ₅ oil 67 Cl chf ₂ CH oc ₂ H ₅ oil 68 F ₂ CH H CH ₃ OC ₂ H ₅ oil 69 f ₂ ch Cl CH ₃ oc ₂ H ₅ oil 70 f ₂ ch Br CH ₃ oc ₂ H ₅ oil 71 CF ₃ CF ₃ CH, oc ₂ H ₅ oil 72 CF ₃ H C, H + n oc ₂ H ₅ oil 73 CF ₃ H ^C 2 ^H 5 oc ₂ H ₅ oil 74 CF ₃ H C, H? Iso OC ₂ H ₅ oil 75 CF ₃ H H oc ₂ H ₅ oil

The following are formulas of two other compounds not included in Table I in terms of efficacy:

Compound No. 76 (oil)

Compound No. 77 (oil)

Many of the compounds in the above table did not disclose physical constants in the form of melting points or boiling points, since these compounds were very often isolated by thin-layer chromatography and largely represent viscous oils. The structure of these compounds was determined from their NMR spectra, which largely correspond to the structures shown in Table I.

The compounds of the invention are herbicides which are generally substantially more potent against grass species than against broadleaf plant species. The disclosed compounds can be used to control undesirable grassy plant species growing alone, or at suitable application rates to control grassy weeds growing among broad-leaved crop plants. The compounds of the invention can be applied to the soil prior to the emergence of undesirable grass species (pre-emergence application), or to above-ground parts of growing grass species (post-emergence application).

Accordingly, the present invention also relates to a method of inhibiting the growth of undesirable plants, especially grassy species, which comprises applying a herbicidally effective amount of a compound of formula I as defined above to the respective plants or to their locus.

The amount of active substance to be applied depends on a number of factors, for example the type of plant whose growth is to be inhibited, but in general, doses of from 0.025 to 5 kg / ha, preferably from 0.1 to 1.0 kg / ha, are suitable. Appropriate application rates will be readily determined by those skilled in the art using routine standard tests without performing any extensive experimental verification.

The compounds of the invention are preferably applied in the form of compositions in which the active ingredient is mixed with a carrier which is a solid or liquid diluent. Preferably, such composition further comprises a surfactant.

For example, the solid compositions of the invention may be in the form of dusts or granules. Suitable solid diluents in the present case are, for example, kaolin, bentonite, diatomaceous earth, dolomite, calcium carbonate, calcium carbonate, powdered magnesium oxide and fuller's earth.

The solid compositions according to the invention may also be in the form of dispersible powders or granules which, in addition to the wetting agent, facilitate the dispersion of the powder or granules in liquids. Such powders or beads may contain fillers, suspending agents and the like.

Liquid formulations include aqueous solutions, dispersions and emulsions containing the active ingredient, preferably in combination with one or more surfactants. Water or organic liquids may be used to prepare solutions, dispersions or emulsions of the active ingredients. The liquid compositions of the invention may also contain only one or more corrosion inhibitors, such as lauryl isoquinolinium bromide.

The surfactants may be of the ionic, anionic or non-ionic type. Suitable cationic agents include, for example, quaternary ammonium compounds such as cetyltrimethylammonium bromide. Suitable anionic agents are, for example, soaps, salts of aliphatic monoesters of sulfuric acid, for example sodium lauryl sulphate, salts of sulphonated aromatic compounds, for example sodium dodecylbenzene sulphonate, sodium or calcium or lignin sulphonate, butylnaphthalenesulphonate and mixtures of diisopropyl-sodium-triisalpha-sulphonate

Suitable nonionic agents include, for example, ethylene oxide condensation products with fatty alcohols such as oleyl alcohol or cetyl alcohol, or with alkyl phenols such as octylphenol, nonylphenol and octylcresol. Other nonionic agents are the partial esters derived from long chain fatty acids and hexitol anhydrides, for example sorbitol monolaurate, the condensation products of said partial esters with ethylene oxide and lecithins.

Compositions intended for application in the form of aqueous solutions, dispersions or emulsions are generally supplied as concentrates containing a large amount of active ingredient. The ge concentrates are then diluted with water before use.

The aforementioned concentrates are often required to withstand long-term storage and, after storage, to be diluted with water to form aqueous preparations which remain homogeneous as long as they can be applied by conventional spray equipment. The concentrates may conveniently contain from 10 to 85% by weight of active ingredient, preferably from 25 to 60% by weight of active ingredient.

Diluted preparations ready for use may contain varying amounts of active ingredient, depending on the intended use. Dilute preparations suitable for most applications contain between 0.01 and 10%, preferably between 0.1 and 1% by weight of active ingredient.

The compounds of the invention can be prepared from the appropriately substituted 2-halopyridines of formula II,

in which

X represents a fluorine, chlorine, bromine or iodine atom;

Y and Z are as in formula I.

The conversion of the halopyridines of the formula II to the compounds of the formula I can be carried out by three general procedures, described below as A, V and C.

Procedure A illustrates the following reaction scheme:

Procedure

OM (II) (III) demethylation reagent such as pyridine hydrochloride (IV) ^and L + H - CH-R ² bases

(1V>

(IN)

2

In the scheme illustrating process A, R, R, Z and Y are as defined above, Hal represents a halogen atom, preferably chlorine or bromine, and M represents a cation, for example sodium cation.

In process A, a suitably substituted halopyridine of formula II is reacted with a metal salt of p-methoxyphenol, for example with a sodium salt of p-methoxyphenol. The reaction is preferably carried out in a solvent or diluent, for example, methyl ethyl ketone, tetralydrofuran, dimethylsulfoxide or dimethylacetamide. The thus obtained 2-p-methoxyphenoxyleervate of formula III is then demethylated by standard procedures, for example by heating with pyridine hydrochloride or hydrogen bromide in acetic acid, to give the corresponding p -hydroxy compound of formula IV which is then in the form of its metal salt, for example sodium or potassium, It is reacted with an appropriate haloalkanoic acid derivative of the formula V to give the desired product of the formula I. This reaction is preferably carried out in a solvent or diluent, for example a methyl ether ketone.

Procedure B shows the following reaction scheme:

(II) + HO

bases ----- (iv) r1

I 1 (IV) + Ha-CH-R ² base (I)

In process B, the appropriately substituted 2-γlogenpylidine (II) is reacted with hydroquinone in the presence of a base to form the β-hydroxyphenoxy compound of formula IV already mentioned in process A. preferably carried out in a solvent or diluent. Examples of suitable solvents include aprotic solvents, for example dimethylformamide. The reaction is preferably accelerated by heating, for example to a temperature in the range of from 50 to 150 ° C. The base used in this reaction may be, for example, an inorganic base such as sodium or potassium carbonate.

The second reaction step of process B is identical to the last step of process A and should not be further described. ,

Procedure C r 1 (II) + HO

OCH ² R base (I) (iv)

In process C, an appropriately substituted 2-halopyridine of formula (II) is reacted with a 2- (p-lydroxyphosphonic acid derivative of formula (VI) in the presence of a base to directly obtain a compound of formula (I) of the invention.

The compounds of formula VI are known per se or can be prepared by conventional methods.

The reaction is preferably carried out in a solvent or diluent. Examples of solvents include lower ketones, for example, the urethane. inorganic bases such as anhydrous potassium carbonate may be mentioned.

The starting compounds of formula (II) used in processes A, B and C can be prepared by various methods. For example, compounds containing a fluorinated alkyl group can be prepared by reacting a corresponding chlorinated compound with a fluorinating agent to exchange some or all of the chlorine atoms Thus, 2-chloro-5-trifluorotrisilpyridine can be obtained by reacting 2-chloro-5-triltrtrililipridine with a reagent, for example, with antimony fluoride in a liquid flutter. so chlorine atoms ·

For example, 2-chloro-5-trichloroisylpyridine can be reacted with a certain amount of antimony trifluoride to form 2-chloro-5-trifluoromethylpyridine. However, this is not a practical disadvantage since the halogen at the 2-position following the conversion of the halopyridine to the compound of the present invention undergoes a fat reaction.

Certain of the chlorinated compounds required as starting substances shows, all the new compounds, such as 2-chltr trilhtomstUrlpyridin 5-2 and _F-3 5-dicULtr trilhtorietUr.pyridin · These compounds also within the scope of species _vynálezu · In addition, these they are useful as intermediates for the preparation of the compounds according to the invention; they are also effective to some extent as insecticides;

The invention also encompasses a process for the preparation of 2-methyl-5-triltrristlriprridine, characterized in that 3-iuropropidine is reacted with chlorine in the liquid phase under irradiation with ultraviolet radiation.

The reaction of 3'-methyluropridine (in free base form or in salt form) with chlorine is generally carried out in an inert organic solvent. A halogenated hydrocarbon such as tetrachloromethane is conveniently used, but other solvents such as hydrocarbons may also be used. ethers, provided that under the reaction conditions do not respond to the origination nepřijatených undesirable byproducts · reaction proceeds at ambient místnooti or lower temperature slowly, and therefore effectively accelerate * by heating · Suitable reaction temperatures potybni e.g. ^kl and ^d of ^d 50 ^d of 13 ° ^C · reaction ^extensible about ^the can gaze ^at reflux ^d zpětrýfa condenser · preferably poojívvdí solvent dry · reagents · 'reaction mixture may be lltrafdatvvýi rays irradiate the aid of a suitable electric lamp, which light of the highest účinnoH may be immersed in the reaction mixture the product usually produces a mixture of products from which the desired 2-chloro-5-trilhtoriethylpyridine can be isolated in a conventional manner, for example by dessillation.

In a more extensive process for the preparation of 2-Ualtgs-3- or -5-trifluoromethylstridines,

2-Ualtgsn-3- or -5-carnitxyppridine ptdгoЪi ^, and reaction with sulfur fluoride in the presence of hydrogen fluoride as further indicated chemically for 2-chloro-5-fluoromethylstyridine:

HF

Compounds containing a difluoromethyl group can be prepared by reacting the corresponding pyridinaldehyde with sulfur hexafluoride according to the following reaction scheme:

The invention is illustrated by the following non-limiting examples. Unless otherwise indicated, all parts in the examples are by weight and all temperatures are in degrees Celsius.

He did

This example illustrates the preparation of a compound of the invention, in particular ethyl-α-4- (5-trifluoromethyl-2-pyridyloxy) phenoxypropionate (Compound No. 3).

(a) Preparation of 2-chloro-5-trichloromethylpyridine

A solution of 2-bromo-5-methylpyridine (55 g) in dry carbon tetrachloride (600 ml) was filtered and then treated with dry hydrogen chloride to give the hydrochloride. The precipitated solid material was disrupted and the mixture was heated to reflux. Dry chlorine was introduced into the boiling mixture for 6.5 hours under irradiation with an ultraviolet lamp inside the reaction flask. The reaction mixture was cooled and, after filtration, evaporated to a pale yellow liquid residue which solidified upon cooling. According to NMR spectrum, this residue is the desired chloro derivative.

(b) Preparation of 2-chloro-5-trifluoromethylpyridine and 2-chloro-5-difluoromethylpyridine g 2-chloro-5-trichloromethylpyridine was heated together with 50 g of antimony trifluoride at 140-145 ° C for 1 hour. The reaction mixture was cooled, treated with ice and concentrated hydrochloric acid and extracted with ether. The extract was washed with water and, after drying over magnesium sulfate, evaporated. The products from several of these preparations were combined and distilled at atmospheric pressure through a short column packed with Fensky rings. The product boiling at 124-154 ° C, which is identified as 2-chloro-5-trifluoromethylpyridine, is collected. The above boiling fractions were redistilled at 2.7 kPa to give 2-chloro-5-difluorochloromethylpyridine, boiling at the above pressure at 82-90 ° C.

(c) Preparation of 2-p-methoxyphenoxy-5-trifluoromethylpyridine

Sodium hydride (4.2 g of a 50% dispersion in oil, washed with petroleum ether) was stirred in 100 ml of dry dimethylsulfoxide, and a solution of 10.4 g of p-methoxyphenol in. 100 ml of dimethylsulfoxide. The resulting mixture was stirred for 30 minutes to form the sodium salt. 15.0 g of 2-chloro-5-trifluoromethylpyridine in 80 ml of dimethylsulfoxide are added to the solution over a few minutes, the mixture is heated at 70-75 ° C for 3 hours and then allowed to cool overnight. According to thin layer chromatography, only one compound is present in the mixture. The mixture is diluted with water to a volume of 1.5 liters and extracted three times with 600 ml of ether each time. The ether extracts were washed several times with water, then with 1M sodium hydroxide solution and finally twice with 200 ml of water each. After drying and evaporating the ether extract, the desired pyridine compound is obtained as a brown oil.

(d) Preparation of 2-p-hydroxyphenoxy-5-trifluoromethylpyridine

A mixture of 10.5 g of 2-p-methoxyphenoxy-5-trifluoromethylpyridine, 100 ml of glacial acetic acid and 50 ml of 48% hydrobromic acid was stirred and heated to reflux for 7.5 hours. The resultant solution was evaporated, the oily residue is stirred with sodium _(sodium bicarbonate and twice shaken out with 300 ml of ether · ether extract i> was shaken with 200 ml of 2M sodium hydroxide solution and then with 150 ml water, the aqueous layers are combined, The mixture was acidified with 2M hydrochloric acid and extracted with ether (2.times.300 ml) and the ethereal extract was evaporated to dryness to give a brown oily product, identified by 2-p-hydroxyphenoxy-5-trifluoromethylpyridine identification.

(e) Preparation of Compound # 3 of Table I

0.22 g of 2-p-hydroxyphenoxy-5-trifluoromethylpyridine, 0.24 g of ethyl .alpha.-bromopropionate and 0.18 g of potassium carbonate in 5 ml of methyl ethyl ketone were stirred and heated to reflux for 2 hours. The reaction mixture was allowed to stand overnight, then filtered and the residue washed with methyl ethyl ketone. The filtrate and the washings were evaporated and the last residual solvent removed under high vacuum from the oily residue. The NMR spectrum of the oily product corresponds to the structure attributed to Compound No. 3.

(f) Preparation of Compound # 8

0.3 g of the product of (e) is dissolved in 15 ml of n-pentanol containing 2 drops of concentrated sulfuric acid. The mixture is refluxed for 3.5 hours, the solvent is evaporated, the residue is taken up in ether, the ether solution is washed with saturated sodium bicarbonate solution, then dried and evaporated to a colorless oily residue which is purified by preparative thin layer silica gel chromatography. in a solvent system consisting of a mixture of petroleum ether (bp 60-80 ° C) and ether in a ratio of 80:20. According to NMR spectroscopy, this product consists of the desired pentylester. (G) Preparation of Compound No. 1

0.14 g of the product prepared in (e) in 2 ml of isopropanol was stirred at room temperature for 1 and 3/4 hours with aqueous sodium hydroxide solution (1.6 ml of a solution containing 1 g of sodium hydroxide in 100 ml of water). The mixture is evaporated in vacuo, the residue is taken up with water, the solution is acidified and extracted twice with 50 ml of ether each time. An oily product is obtained from the ether extracts which is identified by the desired carboxylic acid.

(h) Preparation of Compounds Nos. 2, 4 to 7 and 14

Using the procedure described in (e) above, using the appropriate .alpha.-bromopropionate ester in each case, instead of ethyl .alpha.-bromopropionate, compounds Nos. 2, 4 to 7 and 14 are obtained.

(i) Preparation of 2- [4- (5-trifluoromethylpyridyl-2-oxy) phenoxy] propionyl chloride

1.2 g of the carboxylic acid, prepared as described in (g) above, were refluxed with 20 ml of thionyl chloride for 1 hour, then excess thionyl chloride was evaporated under reduced pressure. The residue was stirred with 8 toluene and the toluene was evaporated in vacuo. vacuum to remove the last traces of thionyl chloride. The desired substituted propionyl chloride is obtained as an oil.

(j) Preparation of Compounds Nos. 17-23

1

0.78 g of the acid chloride prepared as described in (i) above are added to an excess of aqueous ethylamine (20 ml of a solution containing 70 g of ethylamine in 1.00 ml). The excess ethylamine solution is evaporated under reduced pressure, the residue diluted with water and extracted ether The ether solution was washed with 2M hydrochloric acid and water and evaporated to dryness. Recrystallization of the residue from petroleum ether (b.p. 60-80 ° C) affords the desired ethylamide (Compound No. 17), m.p. 96-98 ° C.

18 to 23 were prepared using the appropriate amine in each case instead of ethylamine.

(k) Preparation of compounds Nos. 9 to 13, 15, 16, 24 and 27

0.87 g of the acid chloride prepared as described in (i) above was dissolved in allyl alcohol and heated to 100 ° C for 1 hour. The excess alcohol was evaporated under reduced pressure, the oily residue was washed with water and 2M hydrochloric acid and dissolved in ether. The ether solution was evaporated after drying and the oily residue was purified by thin layer chromatography on silica gel using a solvent system consisting of a mixture of equal volumes of ether and petroleum ether (bp 60-80 ° C). The desired allyl ester (Compound No. 24) was obtained as a colorless oil.

In analogy, compounds 9 to 13, 15, 16 and 27 were prepared using the appropriate alcohol instead of the allyl alcohol.

(1) Preparation of compounds Nos. 25 and 26

0.94 g of the acid chloride prepared as described in (i) above in dry ether containing pyridine (2 ml) is treated with one equivalent of phenol, the resulting solution is allowed to stand overnight, then evaporated and the residue purified by thin layer chromatography. . Compound No. 25 is obtained as a clear oil. Compound No. 26 is prepared in a similar manner.

Example 2

This example illustrates the preparation of 2-chloro-5-trichloromethylpyridine by chlorination of 3-methylpyridine under UV irradiation.

ml of 3-methylpyridine is dissolved in 300 ml of dry carbon tetrachloride, the solution is heated to reflux (ca. 80 ° C) and heated to reflux with a 100 W ultraviolet lamp, producing radiation at a wavelength of 185 nm, located inside the reaction flask. , indicates dry chlorine gas for 3 hours. Preparative thin layer chromatography (silica gel, chloroform-cyclohexane) of a evaporated sample of the solution thus obtained gave 3 major products in a total yield of 10-15%. 2-Chloro-5-trichloromethylpyridine is the desired product in this mixture as identified by NMR spectroscopy. This fact is confirmed by analysis of the resulting solution by mass spectrography. The other two main products are 2-chloro-3-trichloromethylpyridine and di (trichloromethyl) pyridine, present in an amount corresponding to about 1/2, respectively. about 1/10 of the aforementioned base product.

Example 3

This example illustrates the preparation of 2-chloro-5-trichloromethylpyridine from the 3-methylpyridine salt.

The hydrochloride is prepared from 15 g of 3-methylpyridine with 200 ml of dry carbon tetrachloride by treatment with dry hydrogen chloride. The oily mixture thus obtained is heated to reflux with stirring and dry chlorine gas is introduced into the boiling mixture for 4 hours under irradiation with the ultraviolet lamp used in Example 1, placed inside the reaction flask.

The reaction mixture was cooled and separated by decantation into a solution and a greasy solid which, after purification, contained unreacted 3-methylpyridine salt. The above solution is evaporated to a semisolid, greasy material which contains 2-chloro-5-trifluoromethyilayridine according to the thin layer chromatography.

Example. and

This example describes the preparation of 2-chloro-5-trifluoromethylaluminum according to the procedure of Example 1.

A mixture of 23.6 g of 6-chlornikotnnové acid, 37.4 g sulfur tetrafluoride and 18.7 g of anhydrous ^says fluororesin to be in autoH.Éwu. stirring zaliMvá ^8y Odin to ¹²⁰ ° C. mixture was cooled, poured on le ^d and ^p s at ⁰ ° C was neutralized toncent.rovarým h ^ hydroperoxide sulfate. The aqueous ⁴ mixture was extracted. ether, the extracts were washed with water and evaporated to dryness. The residue is ^P odrobí destlaci,. ^{and the} holding is ^ ^ ⁴ оЬ .vroucí fraction ^P s between ¹⁴⁰ and J5 ⁰ ° C. Analysis of this fraction is formed by ^{two-ihlor-5-p} tritluormeУϊyra yrddieem with some 'minostvím 2 - ^^ 01 ^ 5 ^ ^p 1fluliíetíyl yridint.

Example 5

This example describes the preparation of 2-pyrimidoylmethylaluminum by the procedure of Examples 1 to 4.

30.8 g of 2-chloro-thiylcarboxylic acid and 80 g of anhydrous hydrogen fluoride were heated to 200 DEG C. in an autoclave for 10 hours. The reaction mixture was cooled, ice-cooled and neutralized at 0 ° C. The aqueous mixture was filtered and the residue and filtrate was extracted with ether. The ethereal extracts are washed with water and, after drying, the oil is evaporated to an oily residue which is subjected to distillation to collect the fractions boiling at 140-154 ° C. According to the analysis, this fraction consists of 2-trifluoromethylpyridine with a certain amount of 2-fluoromethyl yridine.

P Peak ad 6

This is an example of the preparation of No. 30 of Table I by Procedure A.

(a) Preparation of 2-amino-3-amino-5-methylpyridine

108 g of 2-5-tmdno mθStylpaгidinu in 300 ml of glacial acetic acid under heating at 90-1 ° ^C-0 ° Malu ^P s ^be for mícMní 16 ^{0 g of} bromine in 55 ml of acetic tysel ^. After the addition was complete, the mixture was heated with stirring for an additional 30 minutes and allowed to cool overnight. The precipitated solid product is filtered off. Ice is added and the mixture is maintained at 0 to 10 while maintaining the temperature. 5 ° C does not naturalize with concentrated ammonia. Distillation of solid material, by wicker. water and drying to give the desired piles.

(b) Preparation of 3- (2-chloro-2-carboxylic acid)

145 g of the product of part (a) rozpuusí in 750 ml of conc cMorovo-metal and vnty 45 ⁰ ml. ^The organic solution was cooled to - ¹⁰ ° C ^and SIIS over ⁹⁰ minutes while keeping the interior temperatures and míchkií '-5 54 ^{g of} isotane are added in 450 ml of water. The resulting extended ^ k: is the ^STE 2 ^у ^ ¹ 1п stirred at ^{C o u} interior temperatures while maintaining ^C o ^{d 20} DEG C. concentrated ammonia zalkaMzuje. The precipitated solid was washed with water, dried, dissolved in 1500 ml of ether, washed with 1 M cold sodium hydroxide solution (1M) and then with 2 x 1 ml of water each time and dried to dryness. obtains the desired

3-brlm - 2cCУol ^5-d in íeSíylppli.

20.1016 (c) Preparation of 2,3-dichloro-5-trichloromethylpyridine

64 g of the product of (b) in 650 ml of dry tetrachloride is treated with dry chlorine. The precipitate formed is broken up and the suspension is sieved to reflux and then irradiated with a source of ultraviolet radiation - dry chlorine is added. After 4.5 hours, the mixture is cooled, filtered and the filtrate is evaporated to give the desired product. 2,3-dlchloro-C-tricrlohmethyl-4-pyridine. The mono-mono spectrum corresponds to the structure reported for this compound.

(d) preparing 2,3-Cichloro-n-frenoxytridinodine

1.0 g of the product from paragraph (C) together with 3.0 g of boron antimonitého'30 minutes and heated ⁿ · 170 ° -180 ° C. The mixture was cooled with ice Rozmic and ^d in the Ou extratoje Eraric. The ethereal extracts yielded a brown oil-like material containing a mixture of 2,3-tetrahydro-5-trifluoromethylpyridine and 3-chloro-2-fluoro-5-trifluoromethyltyrimidium, together with a small amount of 2,4-chlorodifluoromethylpyridine.

(e) Preparation of 3-pyrrolidin-2-β-trichloro-phenoxy-55-trifluoromethyltyridine,

To a suspension of sodium hydride (0.6 g of a 50% oil dispersion, purged with petroleum ether) in 30 ml of dry piethethlsulfoxide, was added 1.5 g of p-methoxyphenol and stirred for 15 minutes. of several repeat preparations, as described in (d) above, in 20 ml of Ploerhlsulfide, heat the reaction mixture at 60 ° C for 4 hours, then add further sodium (0.3 g 50% oil dispersion) to the reaction mixture. and 1.38 g of potassium carbonate. After heating for a further 4 hours, the mixture was poured into ice water and extracted with ether (400 ml). The ether extracts are washed with water, diluted with sodium hydroxide solution and again with water, dried and evaporated to give the desired product.

(f) Preparation of 3-chllr 2-p- ^ yPolxyfroolχ 5-toffUloгrrthyltyriP0nu g of the product from paragraph (e), together with 20 g of 6 tyrrpinhyprlchllridu it Pln stare at ^'E 170-180 DEG C. The mixture was cooled, diluted with dilute hydrochloric acid and extracted with ether. The ether extracts gave maalavý Mater !, which purified t ^r rpaiaaiooí ihrlmraolraffí thin layer of silica ^used, the system formed lztluštěPllvehl 6% ethanol-chloroform mv.

(g) Preparation of Compound No. 30 of Table I

0.16 g of the product of (f), 0.3 g of r-ethylbromobromotropate and 0.25 g of potassium nitrite are heated under reflux for 10 hours in 10 ml of methyl ^β- ethyl ketone. The resulting mixture was cooled, filtered and the filtrate evaporated to an oily residue from which it was collected. remove the last residual solvent by heating in vacuum. According to the NMR spectrum, this oily material is composed of compound No. 30, the purity of which is confirmed by gas chromate. topNrti ·.

2,3-Halo-5-chloromethylpyridine is also prepared by the following alternative procedure:

(h) Preparation of 2-iminooЗ-c-h.or-.5-methrltУrrPlou

To 10.8 g of 2-Amino-5-methylthiazolium per 100 l concentrated. of hydrochloric acid, while stirring and maintaining the temperature at 10-15 ° C, command 21 l of 30% hydrogen peroxide. - Upon complete addition the mixture was stirred without cooling for a further 1 1/4 hours, then poured onto 200 g of ice, the aqueous mixture while maintaining fences ^ ⁰ ^ ^l řWávání ^ e ^ ^{d u)} is adjusted ^{p t} tells áoío taneentrovaného _e ammonia to pH 8 to - 9 and extracted 2 * - 300 ol chloroform. The desired extracts are obtained in the form of a yellow solid from the extracts. (I) Preparation of 2-bromo-3-chloro-5-methylpyridine

A solution of 5.7 g of the product of (h) in 50 ml of 48% hydrobromic acid - cooled to -15 to -10 - was added dropwise with stirring dropwise with 2.6 m of bromine, maintaining the temperature at -5 to 0 ° C. A solution of 5.53 g of sodium nitrite in 12 ml of water is added dropwise over 45 minutes, after the addition is complete, and the mixture is stirred at 0 DEG C. for 30 minutes, then poured onto ice. The aqueous mixture is at forging temperature at 0 ° C ^(d trans mission] ^ e ^{d u)} slightly Zalk ^ D.izuje dropwise addition of concentrated ammonia and extracted with - 150 ml of ether. The ethereal extract is washed with water, with sodium bisulphite solution and again with water, dried and evaporated. The residue is taken up in petroleum ether (b.p. 40-60 ° C), the solution is filtered and evaporated. The residue is identified as 2-bromo-3-chloro-5-methyl-pyridine.

(j) Preparation of 2,3-Pihloro-5-chloromethylapyrine

2.9 g of the prodrug from (i) in 250 ml of carbon tetrachloride with dry hydrogen chloride were converted to hydrochloric acid. Chlorine was introduced into the resulting mixture at 80 ° C and after irradiation with an ultraviolet lamp located inside the reaction flask. After 3 hours, - the solvent odppaí thus obtained as residue ^{2,3-dichloro-5-triLUoon8βthylayriPin.}

Example 7 ‘

This example illustrates the preparation of 2,3-dihloro-5-trifluoromethylpyridine by fluorination of 2,3-dihloro-5-methylmethylpyrrine using the fluorinating agent of the alternative reagent of Example 6.

g of 2,3-dichloro-5-trhcЮom ethylpyriPinu ^ 10 hours of stirring in an autoclave to ²⁰⁰ ° ^{C - 100} e ^{- g} ^ tozvoMho the fluororesin. The cooled mixture was poured on!. · ^Ρ and рт! ^T emperature ^{of 0} ° ^C, neutralized with hydroperoxide ^d hy ^d Nym. The aqueous mixture was extracted with 750 ml ^- meetylenchloridu - Extracts - for ^ H 500 yl of water, 500 ml uh.iěittnu - solution and again 500 ml water, dried - and odppaí. The oily residue is subjected to dilution while collecting the boiling fraction. ^{mp -77 to} 83 ° C / 3.3 kw. Wentimovary as the desired amino derivative.

PíkLid 8

This example further illustrates the preparation of 2,3-Pihloro-5-trifluoromethylayrimidine.

g of antimony trifluoride and e, to remove moisture, are melted in vacuo. The cooled material was melted and 6.6 g of antimony chlorine were added thereto while stirring at 65-70 ° C. The SIIC then moats 40 - g of _{2,3-Pihhlor-5-l} trhcLйrmlethylаyriPinu resulting mixture was heated at 45 m.nut 160 ° C and then ocUadí deettluje- with steam. The distilled off oil is extracted twice with 100 m ether each time, the ether extracts are washed with tartaric acid solution, then with water, sodium carbonate and again with water, dried and evaporated. The oily residue is subjected to a fraction boiling at 71-80 ° C / 2.4 kPa, identified as the desired pyridine derivative.

Example 9

This example illustrates the preparation of 3-chloro-5-trifluoromethyl-1-2-P ^and 1-propyrrolidinopyridine by Procedure B.

OL - dry dimethylformaamiPu - gets rid of air by boiling under reflux!

4.95 g of hydroquinone and 6.84 g of anhydrous potassium carbonate are added and the mixture is refluxed for 90 minutes. To the resulting mixture over a · - 4 hours was added 6.48 g ^2, 3-5-Pihhlor triULuomaethylayriPint PimethylOomumiPu 30 ml - degassed, reakěint mixture - was allowed to cool overnight, diluted with 500 m of water, ok ^ ssl! with dilute hydrochloric acid and extracted twice. in 400 ml of ether. The ethereal extracts were transformed twice with 500 ml of water each time, extracted with --300 ml of dilute sodium hydroxide solution, washed with water, the aqueous fractions were combined and again washed with hydrochloric acid. The acidified aqueous solution is extracted twice with 400 ml of chloroform each. The chloroform extract gave a light brown oily ratteiál which upon trituration with petrolehherer (b.p. 30 ^and 4 ⁰ ° C) poslkytne colorless solid ^P roducts, ^the esters of ^p ccording identified as the required 3-chloro-5-iflS0uortθhУyl-P-ny ^ hαr ° Уft ^, nnoyrpyrddntem

Přikladlo r

This example illustrates the preparation of ethyl 2- [4- (3-chloro-5-trifluoromethyl-phenyl-2-oxo) -phenyl] propionate (Compound 6.30 sec - Table I).

1.0 g of the product of Example 9 is boiled under reflux in 25 ml of mercaptoethyl ketone for 4 hours with 0.5 g of potassium carbonate and 1.0 g of ethyl 2-boompropionate. The reaction mixture was discarded, filtered and the filtrate was evaporated. The oil was evaporated to an oily residue which was purified on a thin layer. 20x20 cm plates with a 2 mm adsorbent layer and a mixture of 20 parts by volume ether and 100 parts by volume hexane as solvent system are used. The product was extracted with ethanol. Evaporation of ethanol gave a colorless oily residue identified by Compound No. 30 by NMR spectroscopy.

Example i

The procedure described in Example 10 was followed by the following: Using the 2-bromopropionic acid ester to be prepared in each case, compounds 29, 31 to 39, 41 to 42 of Table I are prepared.

Example 12.

This example illustrates the preparation of 2- [4- (3-chloro-5-trifluoromethyl-pyridyl-2-oxy) -phenoxy] -propionic acid (Compound No. 28 of Table I).

A solution of 0.23 g of sodium hydroxide in 20 ml of water was added dropwise at room temperature to 2.19 g of compound 31 of Table I in 20 ml of isopropanol. The mixture was stirred at room temperature for 4 hours and then diluted to 300 ml with water. The resulting solution was extracted twice with 50 ml of methyl chloride each time and acidified with 2M hydrochloric acid. The acidified solution was extracted with 2 x 140 ml of ethyl acetate, dried, and evaporated to an oily residue which solidified on standing. evný IAEA ^p ^ l ^ skytne ^y su after the measurement ^of vacuum ^p s ^p te ture of 85 ° ^C compound ^Nr. M.p. 104-107 ° C.

Example 13

This example illustrates the preparation of compounds No. 43-45 and 48-51 of Table I.

(a) Preparation of 2- (4- (3-chloro-5-ifluoromethylpyrrole: 1-1-1-oxf) nenoyl) propanol chloride

16.5 g of the carboxylic acid prepared according to Example 12 were dissolved in an excess of thionyl chloride (200 ml) and refluxed for 2 hours. Evaporation of excess thionyl chloride under reduced pressure gave the acid chloride as a yellow oil which was dissolved in 220 mL of dry ether and used to prepare compounds Nos. 40-43-45, 48-51 and 77 as described below. Since these procedures are quite common, only brief details are set forth in the following. tables:

4Γ

201016 16 compound number of the acid chloride solution used reactants and reaction conditions product cleaning 43 20 m 20 ml of aqueous dimethylamine CHTV ⁺ ) at room temperature (siUkagel - ether) 44 20 ml 0.75g mooroline in 20 ml ether at room temperature overnight Recrystallization from petroleum ether (bp 6 ° - ⁸⁰ ° ^C) and toluene 45 20 ml 0.65 g of aniline in 20 ml of ether at room temperature overnight Recrystallisation from petroleum ether ^(boiling point te ^p lota 60- ⁸ 0 ° C and methanol, isopropanol ^n-p) 46 20 ml 6 ml Z-chloroethanoium, 2 hours at 100 ° C CHTV 49 20 ml 0.55 g of p-chlorophenol, 1 ML of pyridine, in 20 ml of ether at room temperature overnight CHTV [silica gel, ether: petroleum ether (b.p. ^60-80 ° ^{C) 'p} omšru volume 1: 5]. 50 20 ml 0.45 g thiophenol, 1 ml pyridine, 20 m ether at room temperature overnight CHTV as in Compound # 49 51, · 1> 5 g of acid converted to chloride 20 ml of 20% aqueous methTlamine at room temperature recrystallization from petroleum ether (bp 60-80 ° C) and toluene

and

Legend:

as described above

0.6 g of acid - 20 ml of ethylene glycol at room temperature for 3 hours as described above

CHTV (SiUkagel - ether) ⁺⁾ CffíV = · thin-layer chromaaoggria

Example 14

This example illustrates the preparation of compound δ.

Table I <

To a solution of 0.95 g of phenylhydrazine in 20 ml of dry ether is added at room temperature 20 ml of the solution prepared in paragraph (a) of Example 13 and stirred overnight. layer was separated, washed with water and dried. Evaporation of ether gave phenylhydrazide. in solid form. Substances melting at 109 to 110 ° C

Example 15

This example illustrates the preparation of Compound # 47 of Table I.

To a solution of 0.25 g of propargyl alcohol in 20 ml of ether containing 0.75 g of potassium carbonate was added 20 ml of the solution prepared in Example 13 (a). The mixture was stirred at room temperature. overnight · Z dhrommaoogeafie sample of the reaction srnmsi shows that there was no response · SMSS was filtered and the filtrate evaporated to an oily residue, to which ^there was added ⁵ ml proparcrlaltotolu and stirred for 2 Todina of ^AHR IV ^{and 100} ° C · reaction It is cooled and the excess proptargrial alcohol is evaporated off under reduced pressure. · The residue is purified by thin-layer chromatography on a thin layer of silicagel in a solvent system consisting of some ether and petroleum ether (b.p. 60 · 60 ° C) in a volume ratio of 1: 5. The product thus isolated is a colorless oil which solidifies on standing to give Compound (47), m.p.

58.5 ° C.

Example 16

This example illustrates the preparation of ethyl α-4- (5-dichloro-chloro-2-pyridoloxy) phenoxy-propionate (Compound No. 52) by Procedure A.

(a) Preparation of 5-difluoro-chloromethyl-22β-methooyphenooypyridine

To a solution of 0.62 g of p-metho-orphenol which had been pre-treated with sodium nitride (0.24 g of a 50% oil dispersion, free of petroleum ether) in 15 ml of dimethyl sulfoside was added 1.0 g of 2-chloro-5-chloro-chloromethyl-pyrimidine 1 (b) in 10 ml dimeehc ·! sulfooidu. Mixture with stirring for 5 hours in ^{the three A} to ⁶⁰ to ^'6 5 ° C, ^p and poured onto ^{L d} and e are extratuje Etterem. The ethereal extracts were washed with water, dilute sodium thyroid and again with water, dried and evaporated to an oily residue which was identified as the desired p-methoxyl derivative.

(b) Preparation of 5-rifluoroorochoromethyl-2-p-rdoooyphenooypyririne

1.0 g of the product of (a) was dissolved in 12 ml of glacial acetic acid and 5 ml of 48% aqueous hydrobromic acid was added. The reaction mixture was refluxed for 3.5 hours, then cooled and concentrated under reduced pressure. The residue was taken up in ether, washed with ethereal sodium carbonate solution and water, dried and evaporated to an oily residue which partially solidified. This residue was purified by prepaa ration on a thin layer of silklcegel in a solvent system consisting of 6% ethanol in chloroform.

(c) Preparation of Compound No. 52

0.18 g of the product from paragraph (b) in 10 ml of m ^ tlt ^! ^ <^ ¹ ^ tt ^ C ^ lke1 nu together with 0.3 g ett ^ l- ^ and ^ «^ t ^ i ^ ( The mixture was cooled, the solid filtered off and washed with ethyl acetate. The filtrate and washings were evaporated in vacuo to an oily residue. , which, according to NMR spectroscopy, is a substance whose structure corresponds to compound No 52.

Example 17

This example illustrates the preparation of ettlp2β [4- (ZrChloro5rflordordororaettflayriryl-2pOoy) phenooylpropionate (Compound No. 53 of Table I) by Procedure C.

A mixture of 1.0 g of 2,3-trifluoromethylpentyl-ethyl-ethylayririne and 1.0 g of ethyl (2- (2-methylphenyl) propionate) in 10 ml of meettlethyl ethyl ketone contains 1.0 g of g-ΙΙΙΠ The mixture was heated to reflux for 3 hours over a period of 2 minutes. After cooling, the mixture was cooled and filtered, the residue was washed with ethyl acetate and the filtrate, together with the wash liquids, evaporated under reduced pressure to an oily residue. is vyččssí rhromatooratfí gel TLC in a solvent system consisting a mixture Etter and petroletteru (b.p. 60-80 ° C) in a volume ratio of 1: 4. to give a colorless oil. product which solidified ztutne for MMN ^also for compounds ^No. enyne ^{y No} . about ⁵³ te ^p lo ^thee Tondo ⁶¹ and ⁶² ° C.

P P.íkl and d 18

This example illustrates the preparation of compounds 54-58 of Table I.

(a) Preparation of proopl-2- [4- (C 2- chloro-5-chlorodiflooreethylpyridyl-2-oxyl) phnooxy] propionate

As described for the ethyl ester in odpooídaajcí · Example 17 was allowed to 2,3-dichloro-5-chlordifluorpyridin reacted with n-propyl-2- (4-ldclrolfennoxy) poppOnntem in eeelu ^г l · ^e tUylketonu. The thus obtained propplester is purified so that rozpussí in SM ^ i ^ JL 1 part by volume of ether and 4 vol ^d ILU ^ trolet ^ ru ^(t ^ e ^p lo ^t and boiling point ^60-80 ° ^C) and ^p odrobí with clurome ^and tgga ^and ii on the silica column.

(b) Preparation of the carboxylic acid from the product obtained in (a)

The propplester prepared in (a) is dissolved in isopropanol and sodium hydroxide solution is slowly added to the solution as described in Example 12. The carboxylic acid was isolated as described in Example 12.

(c) Preparation of the acid chloride from the product obtained in (b)

The 2- [4- (3-chloro-5-chlorodifluoromethylpyrrolidin-22-olyl) phenoxy] poroic acid prepared in (b) was heated at 100 ° C with an excess of thionyl chloride for 2 hours, after which excess thionyl chloride was evaporated reduced pressure. The resulting acid chloride is then used to prepare compounds No. 54-58 as described below. Because these are quite common procedures, the farther reaction is given a brief detail, summarized in the following table:

compound number reaction procedure product cleaning 54 reflux for 2 hours with an excess of 2-chloroethanol CHTV ^x) Leak ^ 1- · ^^) 55. reflux for 2 hours with an excess of aHyl alcohol CHTV (TilikageL-etUsr) 56 Reaction with 0-chlorophenol in ether in presence of pyridine at room temperature overnight the product is practically pure 57 reaction with an excess of aqueous methylamine solution CHTV (tilikagel-etUer) 58 reaction with an excess of o-chlorophenollarzine CHTV (^ mageL-ether)

x 1

Legend: CHTV = thin-layer chromehtgrahie

Example 19

This example describes the preparation of 3-bromo-22-oxo-trifluoroethyl acetate.

(a) Preparation of 3-bromo-2-chloro-5-ethylpyriainic acid 3-bromo-2-chloro-5-pyridoxicarboxylic acid is heated with 650 ml of water containing 60 g of potassium bromide and potassium methanesate. with stirring for 3 hours at reflux. After adding 20 gm ain ^ ^ E ^ and ^ n ^{^,} potassium carbonate the mixture is heated with stirring for another 2.5 hours and then to remove unreacted starting maateiálu subjected to steam distillation and filtered hot. The residue is washed with hot water, the filtrate, together with the liquids, cooled and acidified with concentrated hydrochloric acid. The solid precipitated is extracted with ether, the ether extract is dried and evaporated. To give 3-Broe-2-chloroύl ^Iain 5-karboxllová of acids <

selina.

(b) Preparation of 3-bromo-22-halo-55-trifluoroestrololriain

A mixture of 12 g · of the product prepared in (a), 20 g of sulfur hexafluoride and 10 g of anhydrous hydrogen fluoride was heated to 120 ° C in an autoclave with stirring for 8 hours. The reaction mixture was extracted with ice and neutralized with concentrated sodium hydroxide at 0 ° C. The aqueous mixture is extracted three times with 100 ml of ether each time, the extracts are washed with water, sodium bicarbonate solution and again with water, dried and evaporated to a brown oily residue which is subjected to distillation. A fraction boiling at 88-93 ° C, which is identified by 3-bromo-2-fluoro-5-trifluoromethylpyridine, is collected.

The product prepared as described in (b) is used as a starting material for the preparation of compounds Nos 59 and 60 of Table I by Procedure C.

Example 20

This example describes the preparation of 2,5-dichloro-3-trifluoromethylpyridine and 2,5-dichloro-3-difluoromethylpyridine.

(a) Preparation of 2,5-dichloro-3-trichloromethylpyridine and 2,5-dichloro-3-dichloromethylpyridine

37 g of 2,5-dichloro-3-methylpyridine in 500 ml of dry carbon tetrachloride are treated with a sufficient amount of dry hydrogen chloride to precipitate the hydrochloride of the above pyridine derivative. The resulting mixture is then heated to reflux with stirring and dry chlorine is introduced into the boiling mixture under irradiation with an ultraviolet lamp inside the reaction vessel. Chlorination is carried out for 3.5 hours, then the reaction solution is evaporated to a viscous residue which is washed with petroleum ether (b.p. 30-40 ° C). By identification, this residue is predominantly 2,5-dichloro-3-trichloromethylpyridine. Evaporation of the filtrate yielded an oily material which was identified as predominantly 2,5-dichloro-3-dichloromethylpyridine.

(b) Preparation of 2,5-dichloro-3-trifluoromethylpyridine g of 2,5-dichloro-3-trichloromethylpyridine from (a) in 90 ml of anhydrous hydrogen fluoride was heated under autoclave at 200 ° C for 10 hours. The contents of the autoclave were cooled, poured onto ice and neutralized at 0 ° C with concentrated sodium hydroxide. The aqueous layer was decanted from the oily organic layer and the organic layer was extracted with a total of 750 mL of methylene chloride in several portions. The methylene chloride extracts were dried and evaporated to an oily residue which was distilled. A fraction boiling at 70-76 ° C / 2.7 kPa is collected, which is analyzed by 2,5-dichloro-3-trifluoromethylpyridine containing about 10% by weight of 5-chloro-2-fluoro-3-trifluoromethylpyridine.

(c) Preparation of 2,5-dichloro-3-difluoromethylpyridine g 2,5-dichloro-3-dichloromethylpyridine in 60 g anhydrous hydrogen fluoride was heated at 200 ° C in an autoclave with stirring for 10 hours. The reaction mixture was cooled, poured onto ice and neutralized at 0 ° C with concentrated sodium hydroxide solution. The aqueous layer was poured from the organic layer and the organic layer was dissolved in methylene dichloride. The methylene dichloride solution was used to extract the aqueous layer. The methylene dichloride extract was washed with water, sodium carbonate solution and again with water, dried and evaporated. The oily residue is subjected to distillation to remove the fraction boiling at 85 to 98 ° C / 2.9 kPa, which is redistilled in a rotary column microdistillation apparatus. The fraction boiling at 87-87.5 [deg.] C./36 mbar is identified by identification as 2,5-dichloro-3-difluoromethylpyridine with a purity of 95%.

The 2,5-dichloro-3-trifluoromethylpyridine obtained above was converted to Compound No. 61 and 62 of Table I by Process C and 2,5-dichloro-3-difluoromethylpyridine was converted to Compound 67 by Process C.

Reaction of 2- [4- (5-chloro-3-trifluoromethylpyridyl-2-oxy) phenoxy] propionyl chloride with 2-methoxyethanol, morpholine, aniline, respectively. benzyl alcohol using the procedures described in Example 201016 du 1, (j) and (k), to prepare compounds δ. 63 to 66. The chlorofluoric acid required for these reactions. is prepared by reacting the corresponding acid with thiyl chloroacetate according to the procedure described in (i) of Example 1. The necessary carboxylic acid is obtained by hydrolyzing the saturated sodium hydroxide using the procedure described in (g) of Example 1.

Example 21

This example illustrates the preparation of ethyl 2- [4- ^{(5atilluomeehhyFlpyo,} adyl-220: ιq)) eitl2xy] ooo · propionate (compound no. 68 of Table I).

(a) Preparation of 2-Chloro-5-forryloyrthilag 2-Chloro-5-cyjuoyriatul in 60 ml of 90% formic acid and 15 ml of water are heated to 55 ° C with stirring, 15 ^g of Rannyyni-klu alloy and clay are added, was ^9, 5 hours ríih ^{e p} s at 55 ° C, then filtered hot. The residue on the filter was washed with about 25 ml of warm ethanol, combined and diluted to 600 ml with water. The solution was extracted three times with 250 ml of ether each time, the ethereal extracts were washed with aqueous sodium carbonate solution and water, dried and evaporated to a pale yellow solid residue, which was not shown as 2-halogeno-5-phosphoric acid. .

(b) Preparation of 2-fluoro-5-difluoro-aryl-ethyl-diol

A mixture of 9.9 g of the product from paragraph (a) and 15.5 g of boron siřičiéého was heated 6 hours at utokl ^ u ^ to ^{- 1} 53rd to ¹⁵⁵⁵ ° C. ^ Autoclave was cooled, the pressure samples are released in the mixture zalkakzuje ^d etched with buffered dioxide sodního and extracted rrУtylyndichl · orider. The methyl ethyl dihydrate extract was dried, evaporated and the oily residue was de-distilled. The fraction boiling at 156, and ^from 164 ° C ^{- a} is ^p ^ <^ Ile ^ nent cation formed -ihl2r ^{2-5- difluoro-l} 221: me ^y the ^l l p ^p d ^{r and} NEM-content % of the compound of formula (2), 5-diflorrrythyloyridiol.

(c) Preparation of Compound No. 68

A mixture of 0.44 g of the product of (b) and 0.63 g of tert-2- (4-methyl-2-xyl) formate in 10 g of methyl ketone, containing 0.5 g of potassium carbonate, 5 hours, the ar is heated with stirring to reflux. The reaction mixture was cooled, filtered and the filtrate was evaporated. The oily residue was purified by thin layer iho2mrao2rafií silkagyll in r2zo2lSttalevér system smmsií consisting of 75 parts by volume of chloroform, 25 parts by volume ^ en ^ trol (te ^ ttoí OTA ⁶⁰ and ⁸⁰ ° ^C) and 5 volumes of ethyl clay ^d ^^ ^ ce. In this way the desired product is obtained in the form of an oil.

EXAMPLE 22

This example illustrates the preparation ettyl-2- [4- (3-SУ2m · ^d 55 ^d afll2rreУtylpoτr 2-2xy yl) fyo2xl] -or2ot2uétl (Compound no. 70 of Table I).

(a) Preparation of 3-Sr2m-22chhor-5-i2mfloyriaiul

To 8.6 g of 3-Sr2m 22chh2r-5-kyynpyriaiul in 40 - ml of 90% formic acid and 10 ml of water at 8.0 ^g ^ ^can sktio ¹ phono-nklu and aluminum, a mixture of from ⁶ hours with stirring lie ^ ⁵⁵ ° C to ⁶⁰ ° C, then left to stand for two days, then film. The filtrate was diluted with water to a volume of 500 ml and extracted twice with 250 ml of ether each time. The organic extract was washed with aqueous sodium bicarbonate solution, dried and evaporated to an oily residue which was diluted with toluene and then evaporated under reduced pressure. The residue is diluted with a small amount of ether, the solution is filtered and the filtrate is evaporated to an oil, ideotifiable as the desired aldehyde.

(b) Preparation of 3-So2m-22cihooo · 5-aifluorryttyloyrtdiIll

A mixture of 5.6 g of the product of (a) and 9 g of sulfur hexafluoride was heated in an autoclave at ¹⁵⁰ ° C for 6 hours. AutokHv the button ^to be released and ^the contents are autolklúvu Rita · ^p · sodinř uiličitan aqueous solution was extracted with methylene dichloride extract was dried methhlendichloridový odppří and the oily residue which was subjected desstlaci under reduced pressure. The fraction boiling at ^85-9 5 ° C / 2 kPa, ^the esters of ^p ccording i ^ ntifikace formed 3-toom-2-cllor-5idifluomletlyl ^p yridineш, obsahhjícím small možžtví 2-chloro-3-fluoro-5-iffluormttlhУpyridinu or its 2-fluor-ZincchorSuomsru.

(c) Preparation of Compound No. 70

A mixture of 0.5 g of the product of (b), 0.465 g of ethyl 2- (4-hydroxyprenoxy) propiooate and 0.5 g of potassium carbonate in 10 ml of methyl ketone is stirred and heated to reflux for 5.5 hours. The mixture was filtered and evaporated to a yellow oil. The residue was purified by thin layer chromatography by tilica gel using the solvent mixture described in paragraph (c) of Example 21. The main belt was extracted with ethanol. Evaporation of the ethanol yielded an oily product which, according to the gas chrumatigratite, contained 96% by weight of ethyl acetate, which, according to Race NMR, was the compound No. 70.

Example 23

This example illustrates the preparation of ethyl 2- [4- (- chloro-5-difluoromethyllyltriyl-2-oxy) phenuxyl] prupiooate (Compound No. 69 of Table I) by Procedure C.

(a) Preparation of 2,3-iuril-5-ylmethyl-pyrlylpyrrole The 2,3-iiclur-5-hydroxy-glycolic acid containing a small amount of 2,3,5-trifluoropyridia was then autoclaved with 4.5 g of fluoride for 6 hours. To the cooled traction mixture was added aqueous sodium hydroxide and the mixture was extracted with methylene dichloride. The extract was dried and evaporated and the residue distilled in a rotary column microdistillation apparatus. The fraction boiling ^p s and ^{65 from I-00} DEG C. ^p era ccording ^pl ^ ^y ^ n b ^s Chrůma ^and Toor · ogrrfit mixture of about ^60% 3 -chloro-2-fjuurpyriiiou and 40% of the desired 2,3-iicllur- ^5-p iifjgormttlyl yriiiou.

(b) Preparation of Compound No. 69

A mixture of 0.65 g of the product of (a) and 1.0 g of ethyl 2 - (- 1-hydroxyl-phenoxy) -propioate was stirred and refluxed in ml of methyl ether for 4 hours with stirring. The resulting solution was filtered and the filtrate was evaporated to an oily residue which was purified by chromatography on a thin layer of silica gel using a solvent system consisting of a mixture of 75 parts by volume of chloroform, 25 parts ^by volume each ^. t ^tl ^^ lotto boiling TRJ ⁶⁰ and ⁸⁰ ° C) and 5 parts by volume of ethyl acetate. The washed product is a mixture which is rechromatographed using a solvent system consisting of a mixture of 1 volume ether and 2 volumes petroleum (bp 60-80 ° C). There are two belts from which it progresses faster! is extracted with ethanol and the extract is ethanol. odppaí. The oily residue, according to NMR spectroscopy, is composed of Compound No. 69.

Example 24

This example describes the preparation of 2-chloro-3,5-bistrifluorosilylpyriin.

(a) Preparation of 3,5-bit-trifluoromethyl-pyrrolidine 7.5 g of 3,5-pyridinedicarbuxyl acid, summarizing! a poddl pyriiio-3,5-ii ^to trbuxylové acid together with 72 g NaF, and 40 g of HF was heated in 8 hours autold-suture on íspIoíu ¹ 5 ⁰ and ¹⁵¹ ° C. '· Reakfcoí The cooled mixture ^P s ^0C oeejraaizuje concentrated sodium hydroxide solution, the resulting mixture was extracted metihrlendichluridem extract dried and odpaH. The residue is subjected to filtration, collecting a fraction boiling at 119 DEG -128 DEG C., which, according to NMR spectroscopy, consists of a mixture of 3,5- and 2,5-bis-tri: S-dimethylthiopyridines.

(b) Preparation of 2-chloro-3,5-bis-t-fluoromethylpyridine

To a solution of 3.0 g of the product prepared above in 250 ml of dry THF is added a stream of dried chlorine while slowly stirring, refluxing and irradiating the lamp with a lamp. After 6.5 hour the tttrachOomltthan udddeeilsjt and the residue ^^ d st is burned in distillation and ^p ra rotary column. Response system is ^{f p} s boiling ^75-8 5 ° C under identifkkact tter is formed by 2-chloro-3,5-BKS iflSOuoíeeUlyfPpyriineβí containing a - p ^ C ^ dl-2,5- and 3,5-bie triSloirmtthylpyiiěins.

The 2-chloro-benzotrifluoromethylpyridine thus obtained was converted to compound No. 71 of Table I by Procedure C.

Example 25 This example illustrates the preparation of Compound No. 76. x

1.0 g of 2- (p-hydroxy-5-trifluoromethyl) -5-trifluoromethylpyrrine was heated to reflux for 3 days with 1 molar equivalent of 2-chloropolyoltrils and 1 g of potassium carbonate. The mixture was filtered, the solvent odpaíří under reduced pressure and the oily residue vyčissí chromate ^ orrafií tlc eilikagtlu for pouužtí solvent system equal-volume ^D I ^profiles e ^th interruption and kerosene ™ (t-lota bp 60 80 ° C) .

Example 26

This example illustrates the preparation of Compound No. 73.

A mixture of 1.25 g of 2- (p-hydroxyethyl) -5-trifluoromethylpyrrolidine _> 0.75 g of potassium carbonate, 0.96 g of α-bromobutyric acid and 25 ml of trifluoromethyl ketone was heated for 6 hours. boiling under a reflux condenser. The cooled reaction solution is filtered and the filtrate is evaporated to an oily residue which is purified by chromatography on a column of eluent using a 20% by volume ether / hexane mixture. Compound No. 73 is obtained as a colorless oil.

As described above, compounds 72, 74 and 75 are prepared in place of the ethers of .alpha.-bromo-butyric acid, instead of the ethyl ester of .beta.-bromoalkanoic acid. ethyl .alpha.-bromoacetate and ethyl .beta.-bromoacetate.

Example 27

This example illustrates a herbicidal homeland. of the compounds of the invention (compound of Table I).

For test purposes, the compounds are mixed by mixing 5 ml of an emulsion prepared by diluting 100 ml of methylcyclohexane solution at a rate of 21.8 g / l of sorbent monohydrate surfactant (Span 80) and 78.2 g / ml. 1 surfactant based on the condensation product of sorbctin mono-aurate's 20 moles of ethylene oxide (TWeen 20), with water to a volume of 500 ml. The mixture of drug and emulsion is shaken with glass beads and diluted with water to a volume of 12.

The spray preparation thus prepared is possible to spray young plants in pots (postemergence test) at a rate of 1000 l per pot. The types of experimental Ioseln are shown in Table XI. 14 days after spraying, compared to untreated plants, the degree of damage to the treated plants was determined using a 0 to 3 scale, where 0 represents no effect and 3 represents 75% to 100% destruction of the plants.

When testing the herbicidal activity at ^p reemmrgennní, seeds of the test species were placed on the surface of fiber trays of soil and poosříkají with the compositions at hížžsví odpooíddjícím 1000 litůům per hectare. The seeds are then plowed with additional soil. After 3 weeks after the condition, the condition of the seedlings in the treated dishes is compared to that of the untreated control dishes, and the scale is removed using the scale of 0 to 3 above.

The results obtained in the above tests are summarized in Table II below. A dash (~) indicates that the test has not been performed in this case. Preemmogenic application is indicated by the letter A, postemergene application by the letter B. The test plants are referred to as symmoles with the following meanings:

S = salad

R = tomato

Ov / Av = oat and deaf oats (Avena fatu ^ deaf oats is used in the posttesting test, oat in the pre-emergence test

LI =, Lolivrn perenne

Cn = Cyperus rotundus

St = Setaria viridis

The results shown in Table II clearly illustrate the selectivity of the compounds of the invention since the grassy rosslin species used in the test are severely damaged or destroyed, whereas dicotyledons are not substantially damaged.

Table compound number II application rate (kg / ha) method of application WITH R Or / Av IF experimental plants Cn St 1 0.4 AND 0 0 2 3 0 3 (B) 0 0 0 0 0 0 5 0.5 AND 0 0 3 3 0 3 (B) 0 0 3 3 0 3 8 0.4 AND - 0 3 3 0 3 (B) - 0 3 3 0 3 17 0.8 AND 2 0 3 3 0 3 (B) 0 0 3 3 0 3 18 0.8 AND 0 0 3 3 0 3 (B) 0 0 3 3 0 3 19 Dec 0.8 AND  0 0 3 3 0 3 (B) 0 0 3 3 0 3 20 May 0.8 AND 0 0 3 3 0 3 (B) 0 0 3 3 0 3 21 0.8 AND 0 0 3 3 0 3 (B) 0 0 3 3 0 3 22nd 0.8 AND 0 0 3 3 0 3 (B) 0 0 3 3 0 3 23 0.8 AND 0 0 3 3 0 3 (B) 0 0 1 3 0 3 24 0.08 AND 0 0 3 3 0 3 (B) 0 0 1 3 0 3 25 0.08 AND 0 0 2 3 0 3 (B) 0 0 3 3 0 3

201016 24

Compound number application rate (kg / ha) method of application WITH R Ov / Av experimental plants IF Cn st 26 0.08 AND 0 0 1 3 0 3 (B) 0 0 3 3 0 3 27 Mar: 0.08 AND 0 0 0 3 0 3 (B) . 0 0 3 2 0 3 29 0.08 AND 0 0 3 3 0 3 (B) 0 0 3 3 0 - 31 0.25 AND 0 0 3 3 0 3 (B) 0 0 3 3 0 3 41 0.08 AND 0 0 3 3 0 3 (B) 2 0 3 3 1 - 43 0.8 AND 0 0 3 3 0 3 (B) 0 0 3 3 0 3 44 0.8 AND 0 0 3 3 0 3 (B) 0 0 3 3 0 3 45 0.8 AND 0 0 3 3 0 3 (B) 0 0 3 3 D 3 46 0.8 AND 0 0 3 3 0 3 (B) 0 0 3 3 0 3 47 0.8 AND 3 0 3 3 0 3 (B) 0 0 3 3 0 3 48 0.08 AND 0 0 3 3 0 3 (B) 0 0 3 3 0 3 49 0.08 AND 0 0 3 3 ' 0 3 (B) 0 0 3 2 0 3 50 0.08 AND 0 0 3 3 0 3 (B) 0 0 3 0 0 3 51 0.8 AND 2 0 3 3 0 3 (B) 0 0 3 3 0 3 52 0.4 AND - 0 1 0 0 2 (B) - 0 3 2 0 3 53 0.08 AND 0 0 3 3 0 3 (B) 0 0 1 0 0 3 59 0.08 AND v 1 0 2 3 - 3 (B) 0 0 2 3 0 - 60 0.08 AND 0 0 3 3 0 3 (B) 3 0 3 3 0 - 61 0.08 AND 0 0 0 3 0 2 (B) 0 0 3 2 0 - 62 0.08 AND 0 0 0 3 0 0 (B) 0 0 0 1 0 - 73 10.0 AND 3 0 3 3 0 3 (B) 1 0 3 . 3 0 3 74 10.0 AND 0 0 0 3 0 3 (B) 0 0 3 3 0 3 75 10.0 AND 2 0 3 3 0 3 (B) 3 3 3 3 0 3 76, 0.5 AND 0 0 3 3 0 3 (B) 0 0 3 3 0 3 77 0.08 AND 0 0 3 3 0 3 (B) 0 0 0 0 0 -

Example 28

This example illustrates the herbicidal properties of the compounds of Table I. The tests were carried out as described in Example 27.

For test purposes, the compounds are treated by mixing an appropriate amount of the active compound with 5 ml of emulsion prepared by diluting 160 ml of methylcyclohexanone solution, 21.8 g / liter of sorbitan monolaurate surfactant (Span 80), and

78.2 g / l of condensation surfactant with 20 moles of ethylene oxide (Tween 20), water to a volume of 500 ml. The active compound / emulsion mixture is shaken with glass beads and diluted to 40 ml with water. Polymeric plants are prepared using a scale of 0 to 5, where 0 represents 20% damage and 5 represents complete destruction of the plants.

The results obtained are given in the successor to Table III. A dash (-) indicates that the test was not performed in this case. Preemmirgent application is denoted by the letter A, postemergence by the letter B. The test plants are denoted by symbols with the following meanings:

RC = sugar beet

Ø = canola

Ba = cotton _s

So = soya

Ku = maize

Op = winter wheat

Rice = rice

Sn with Senecio vuugaars (Ragwort)

Ip = Ipomoea ppurpuea.

Am = A ^ e ^ i ^ i ^ i ^ -thus retrofeexus

Pi = Polygonem aviculare

Ca = Chenopodium album

Po = Portulaca oleracea

Xs = Xanthium spinosum

Ab = Abuuilon. theopp ^ asii (abuuilon)

Cv = Connolvulus ami ^ is (Field Bindweed)

Ov / Av = common oat and deaf oat (Avena fatna); Deaf oat is used in the post-emergence test, oat sown in the pre-emergence test

Dg = Digita ^ a tenϋgUnoait

Pu = Poa annua

St = Setaria v ^ ridis

Ec = Echinochloe (Saika's Corn Leg)

Sh = Sorghm halepense

Ag = Agropyron eppens,

Cn == Cyperus rounndus.

Table III compound applied to the experimental plant method

number dose (kgha) application Se Ř Ba Sat Ku Op Rý Sn Ip Am Fri Ca After Xs > 1 0.4 AND 1 0 0 0 5 5 5 - 0 0 0 0 0 0 (B) 2 1 0 0 5 3 3 0 0 0 0 0 0 0 5 0.5 AND 0 0 1 0 5 5 5 1 1 1 0 0 0 3 2 (B) 0 0 0 0 5 4 3 0 0 0 0 0 0 0 8 0.4 AND 0 0 0 1 5 5 5 - 0 0 0 3 0 0 (B) 2 2 1 0 5 4 4 0 0 0 0 0 1 0 30 0.4 AND 0 0 1 0 5 5 5 - 0 2 1 0 1 0 B ' 1 0 1 0 5 5 5 1 0 0 0 0 0 0

compound number application rate (kg / ha) method of application i íe S Ba Sat experimental plants Fri Ca Po Xs Ku Op Rý Sn ip Am 31 0.08 A 1 ? 0 0 0 4 4 5 0 2 0 0 0 0 0 b; 1 0 0 0 5 3 3 2 1 0 0 0 0 - 52 1.0 A < ) 0 0 0 4 5 5 - 0 1 0 0 1 0 'B ( ) 1 2 0 5 4 4 ¹ 0 0 0 0 2 0 53 1.5 and ·: 3 0 0 1 4 5 5 0 0 3 0 1 o 0 (B) i 0 1 0 5 4 4 1 0 3 0 1 2 0 59 0,5 ' and: 1 1 0 0 4 4 5 2 0 1 0 0 0 - B ( ) 1 0 0 5 3 3 0 0 0 0 0 0 0 60 0.5 and: I 0 0 0 4 4 5 2 0 0 0 2 0 - B ( ) 0 0 0 5 3 3 0 0 0 0 1 0 • 0 61 1.0 A ( ) '0 0 0 4 2 2 2 0 0 0 0 1 - (B) 1 1 1 0 5 3 2 0 0 0 0 0 1 1 62 1.0 A ( ) 0 0 0 3 4 5 0 0 0 0 2 0 - B ( ) 2 0 0 5 3 2 0 0 0 0 0 1 0 67 1.0 AND 1 0 0 0 4 5 5 2 2 0 0 0 - 0 B ( ) 0 0 0 5 4 3 1 0 1 0 0 0 - 72 1.5 A í '0 0 0 2 0 1 0 0 1 0 1 0 0 B ( ) 0 0 0 1 0 0 0 2 0 0 0 0 0 compound aplikovaná way experimental plants number dose application Ab Cv Ov / Av Dg · Pu St Ec Sh Ag Cn (kg / ha) 1 0.4 AND 0 - 4 - • 4 4 5 5 5 0 (B) 0 0 4 3 0 3 5 5 3 0 5 0.5 AND 1 - 4! > 0 4 5 3 3 1 (B) 0 0 4: 3 0 4 5 5 3 0 8 0.4 AND 0 - 4 - - 3 4 5 4 5 0 (B) 0 - 4 ‘ l 1 4 5 5 4 0 30 0.4 AND 2 - 5 - • 4 ' 5 5 5 5 0 (B) 1 - 5 5 3 5 5 5 5 0 31 0.08 AND 1 - 4 5 4 4 4 3 0 0 (B) 0 0 3-2 5 5 5 4 0 52 1.0 AND 0 - 3 - 1 4 5 4 5 0 (B) . 0 - 4 t l 0 4 5 5 2 0 53 1.5 AND 0 - 4! 5 5 5 5 • 4 2 0 (B) 0 0 5! 5 4 5 5 5 4 0 59 0.5 AND 0 - 4! > 5 5 5 5 2 0 (B) 0 0 5 < l 3 5 5 5 4 0 60 0.5 AND 0 - 4 5 4 5 5 5 4 0 (B) 0 0 4 4 3 5 5 5 4 0 61 1.0 AND 0 - 4! > · 1 5 5 - 4 0 (B) 1 0 3 * 1 2 4 5 5 3 0 62 1.0 AND 0 - 4 5 2 5 5 4 2 0 (B) 0 0 4 ' 1 2 5 5 4 2 0 67 1.0 AND 0 - 5! 5 4 5 5 4 1 2 (B) 0 0 3-3 5 5 5 4 0 72 1 »5 AND 1 - 0 1 0 0 2 0 0 0 (B) 0 0 0 0 · 0 0 0 1 1 0

This example further illustrates the selective herbicidal activity of the compounds according to the invention. The tests are carried out on a number of useful plants and weeds, the active compounds being applied to the useful plants at a ten-fold higher dose than the weeds.

Damage is evaluated in 20 days of possession using a scale of 0 to 10, where 0 means no effect and 10 complete rossiin destruction. · Each of the results shown in the table below represents the average of three rossiin damage. of the herbicidal compounds according to the invention, since even though these compounds were applied to the useful plants at a ten-fold dose than that which led to severe damage to the grass species of the experimental rossiins, there was little or no damage to the useful rossiins.

Meanings of all abbreviations and symbols that the symbol · ΆΓ · indicates a field fox

Table I In the successor table are shown in Example 28 with (Alopecurus myosurodes) ·

F compound number dose applied (kg / ha) for crops + weeds 2 0.25 + 0.025 3 0.5 + 0.05 4 0.75 + 0.075 5 1.0 · + 0.1 6 0.25 + 0.025 7 0.5 + 0.05 6 0.75 + 0.075 9 0.71 + 0.1 10 0.25 + 0.025 11 0.5 + 0.05 12 0.75 + 0.075 13 1.0 + 0.1 14 0.25 + 0.025 15 Dec 0.5 + 0.05 16 1.0 + 0.1 26 0.125 + 0.0125 29 0.25 + 0.025 30 ' 0.5 + 0.05 31 1.0 + 0.1 32 0.125 + 0.0125 33 0.25 + 0.025 34 0.5 + 0.05 35 0.75 + 0.075 , 36 0.125 + 0.0125 '37 0.25 + 0.025 36 0.5 + 0.05 t 39 0.75 + 0.075, 9 40 0.125 + 0.0125 41 0.25 + 0.025 42 0.5 · + 0.05 Example 30

crop plants weeds Sat Ba Sc Ec »6 Av AI 0 0 0 3 2 2 3 0 0 0 4 3 1 1 3 - 0 9 9 6 6 3 1 1 9 9 6 6 0 0 0 6 5 2 0 0 0 0 6 9 1 6 1 2 0 9 9 5 9 0 · 0 0 9 9 3 6 0 0 0 1 0 0 0 0 0 0 7 6 1 4 0 2 1 9 9 6 9 0 0 0 9 9 6 9 0 0 0 5 7 2 3 0 0 2 9 9 4 6 0 0. 0 9 9 5 9 0 0 0 2 1 1 1 0 0 0 9 9 6 2 0 1 0 9 9 9 6 1 3 0 9 9 9 6 0 0 0 2 4 4 0 0 0 0 9 9 6 4 0 1 0 9 9 9 9 0 2 1 9 9 9 6 0 1 0 6 6 5 2 0 0 0 2 3 6 0 0 1 0 9 9 9 6 0 0 0 9 9 9 5 0 0 0 4 4 5 0 0 0 0 9 9 6 5 0 0 0 9 9 9 7

This example illustrates the herbicidal activity of the compounds according to the invention against perennial grass species, as compared to a known herbicidally active substance of a similar type.

This known comparator is Compound A corresponding to the structural formula

Compounds No. 5 and 31 of Table I are compared to Compound A.

In this test, parts of the rhizomes of Sorghum halepense, 5 to 8 cm long, and containing 2 to 3 shoot nests, are buried in the compost presented in plastic trays in a greenhouse. For the purpose of the test, the active ingredients are formulated as described in Example 28. In the pre-emergence test, the active ingredient-containing compositions are sprayed with the compost in the trays three days after the rhizomes have been buried. In the post-emergence test, parts of the rhizomes are left in the soil for 20 days until the shoots with 2-4 true leaves are sprayed and sprayed. Evaluation of herbicidal efficacy is carried out 3 weeks after treatment ·

In this test, each treatment is carried out in three separate experiments. · Results are expressed in percent of plant damage, giving the average of two separate tests.

Preemergence test results compound applied dose (kg / ha)

number . 0.125 0.25 0 »5 1.0 AND 1 1 55 69 100 ALIGN! 5 58 98 100 ALIGN! 98 31 85 88 100 ALIGN! 100 ALIGN!

Results of post-emergence test

compound application rate (kg / ha) number 0.125 0.25 '0.5 1.0 AND 58 85 94 100 ALIGN! 5 66 88 100 100 ALIGN! 31 96 100 100 100 ALIGN!

The results of the above tables show that the compounds of the invention are, at lower doses, more herbicidally more effective than the comparative compound A.

Claims (6)

A herbicidal composition comprising, as an active ingredient, a pyridine derivative of the formula I, in which each of Z and Y represents a fluorine, chlorine, bromine, iodine or hydrogen atom; a diflooromethyl group or a chlorodifloroethyl group, provided that at least one of Z and Y is Uαtgenomethyl trace, R ^1, A represents Al or walk ^^ hydrocarbyl of 1 ^and 4 it aUmy Uh ^ ap R 6 represents cyantstopine, a carboxyl group, carioxamides ^{to the} formula ^- CNR ³ R ⁴ II About where R ³ represents ^and atoms or walk al ^ lo ^ ou quick match with ^{is from 1 to 4} carbon uhHto and R ⁴ represents hydrogen water ^á ^^ quick match stylish ^{1 and 4} carbon ulhtto ^{p p} lean and ^DE substituted Uydroxrltvtu StopIN or phenyl, phenyl, ^p cUlorfenylovtl hundred i5 6 5 Nu, C 1 'to 4 carbon atoms or a group formula -NRR, where R 'is hydrogen or walk * αl ^KRL TV ^and quick match with ^{is from 1 to} 4 carbon UiHto and R is a hydrogen ^vtdíto, al ^to R ^t in ^g quick match with 1-4 carbon atoms, phenyl or chltrfsnrltvá quick match, ^kd or e group consisting ^{of p-N r3r4} yrro ^TiDi NT- p ^ ^ip ^ i id ⁱ no no ^b · ^P of motfolinosto ^INL, or a radical of the formula R -CSR ⁷ II o wherein ^R7 is ^plated with altylovou quick match. ^{1 and} 4 and ^y ^^ m uhHto Neto. ^ hyal trace or R 6 represents an alkaloxycarbonyl tracein wherein the altoxyl moiety contains 1 to 8 carbon atoms may be straight or straight. branched and optionally carries one subitiiusnt selected from hydroxyl zαhrnující StopIN, alktxrstopiny having 1 to 4 carbon atoms and halogen, or carries it sah ^ ^p ^^ td ooVdadjcí above formula I, in ^the structural mechanics ^{R2 is different} from ^{b to} yte -0- ° ^ o ^ no ^b represents of ^the formula ^b yte ° C _(about 0 ° C CH,), C> ^R8 and ² ° ^г where 8 ' R is C 1-4 alkyl and n is 1 to 5, or is cyclic hexyloxycarbonyl, optionally substituted by a halogen atom or a methyl trace, wherein the alkenyl moiety contains from 3 to 6 carbon atoms, phenyloxycarbonyl, optionally substituted with a halogen atom or a methyl halide, or benzylcarbonyl, the phenyl moiety optionally substituted by a halogen atom or a methyl halide, 9 or a salt thereof. a derivative when R is a carboxyl group 2 · The composition according to item 1, reads ^^ jc! characterized in that it contains, as the active substance, a compound of the formula I in which ‘Z is triflt (had typhoid trace, Y is hydrogen, ⁱ is methyl, and ^{J is} 2 · R is a tritin or an al (xx) and al (xx) moiety in which the altoxyl moiety contains 1-6 carbon atoms, ⁿ eb ^of its salt where ^Z e ^{R2 is?} Tortoxylovou with ^the 1lpl ^nu. 3. A composition according to claim 1, wherein the active ingredient is a compound of formula (I): From the trffStoeIseUyY group, Y is chlorine, ^R1 Eetu ^{l hunt} group and ou R is a carboxyl group or an alkoxycarbonyl group in which the alkoxy moiety contains Or a salt thereof when R is a carboxyl group. 4. A composition according to claim 1, wherein the active ingredient is a compound of formula (I): Z difl ^ l ^ o ^ c ^ m ^ ith ^ jL ^ ooo ^ u or cULordffLuoemeUùyOooou group, Y atmui vodka or chlorine, ^r1 metal. group and R is a carboxyl group or an alkoxycarbonyl group in which an aloxylol. part contains 1 to 6 carbon atoms, o or a salt thereof when R is a carboxyl group. 5. The composition of claim 1, wherein the active ingredient comprises buuyL- -2- [4- triUOuormeUllr to I5-2-ols alytoly _Γ) ennoxy] ^^ for sulfonate. · 6. The composition of item 1, wherein: characterized in that it contains as active ingredient propyl- -2- [4- (3-chloro-5-trifluoromethyl-2-olyralololyl) oxo] propionic acid;