NL7904242A - METHOD FOR PREPARING A PYRIDYLOXYPHENOXY UNSATURATED DERIVATIVE AND ITS USE IN A HERBICIDAL COMPOSITION - Google Patents

Description

'E\. . «-1- 20676 / Vk / iv

Applicant: Kumiai Chemical Industry Co. Ltd-., Tokyo, Japan.

Short designation: Process for the preparation of a pyridyloxyphenoxy unsaturated derivative and its use in a herbicidal composition.

The invention relates to a process for preparing a pyridyloxyphenoxy unsaturated derivative. The invention further relates to the use of this derivative in a herbicidal composition and the pyridyloxyphenoxy derivatives thus prepared and the herbicidal compositions obtained.

The method according to the invention for preparing a pyridyloxyphenoxy unsaturated derivative is characterized in that the derivative of formula 1, indicated on the formula sheet, wherein Z represents -CHgOH, C00R or -COSR »and R represents a hydrogen atom, organic or inorganic salt alkyl, haloalkyl, -alkenyl, alkynyl, phenyl, halophenyl, alkylphenyl, benzyl, alkoxyalkylenoxyalkyl, pyridylmethyl or alkoxyalkyl and R * is an alkyl group prepared by an unsaturated halide of Formula 2, where Z 'has the meaning of Z or a group which can be converted to Z, and Hal represents a / halogen atom, to react with a pyridyloxyphenol of formula 3, indicated on the formula sheet, in the presence of a hydrogen halide extracting agent such as a base , at a temperature of 0-150 ° C and, if desired, Z * is converted to Z by an esterification, a hydrogenation, neutralization or an amidation.

The invention also relates to the herbicidal compositions containing the compound of formula 1 as an active component.

Very recently, a number of herbicides have been proposed and used to reduce the work that needs to be done differently in agriculture.

Thus, a number of problems have been brought about by the herbicidal influences and the safety of application of the herbicides has played a role in their practical application.

Therefore, search has been made for improved herbicides which do not adversely affect the desired plants and which have an effective effect on the noxious weeds when the active component is used in a small dose and are significantly safe without causing environmental pollution.

. The pyridyloxyphenoxy unsaturated derivatives developed have been found to be suitable for herbicides and the herbicidal influences of these derivatives have been investigated.

7904242 ...... - /: .....

-2-20676 / Uk / iv

The novel pyridyloxyphenoxy unsaturated derivatives of formula 1 of the invention have very good herbicidal activity against noxious weeds such as barnyard grass, crab grass and Johnson grass as compared to compounds as described in Japanese Patent Application No. 131540 1977 such as <* -] [4- (3,5-dichloropyridi-2-yloxy) phenoxyvaleric acid derivatives, especially the methyl and isopropyl esters or the sodium salt and as described in Japanese Patent Application No. 48432/1976, and 87173 / 1977 such as <x-jA- (3,5-dichloropyrid-2-yloxy) phenoxy] propionic acid derivatives such as the methyl and ethyl esters or the ammonium and sodium salts.

The new compounds of the invention also have superior herbicidal activity compared to butoxyethyl ot - [] 4- (3,5,6-tri-chloropyrid-2-yloxy} phenoxypropionate as shown in Japanese Patent Application No. 15382 / 1978.

The new compounds of the invention have a better residual activity in the soil in a soil treatment and have an excellent influence such as a long suppression of weeds at a later stage.

Long suppression of recovery from incomplete weed suppression in foliar treatment, control of growth of grown weeds and excellent stability to various factors. For varying the activity caused by rainfall, atmospheric moisture and high temperature with stable activity.

The new compounds of the invention have a methyl group in the position of the pyridyloxyphenoxyisobutgnyl compounds, the special herbicidal influence particularly the significant herbicidal influence over noxious weeds such as Johnson grass, foxtail, barnyard grass and tall crab grass can be improved.

The new compounds of the invention have significant selectivity without phytotoxicity over broad-leaved plants such as radishes, soybeans, adzuki beans, groundnuts, cotton, flax, beets, sugar beets, potatoes, colza, sweet potato, cucumber, olive, Chinese cabbage, lettuce, tomato, egg plant, radish, onion, watermelon, strawberry, pimento, sunflower, tea, coffee, rubber, peppermint plant, hops and tobacco plants, but full control of harmful weeds.

The new compounds of the invention can be administered as herbicides according to desired methods in any season such as a ground treatment 790 4 2 42 • tr * -3- 20676 / Vk / iv T * and a leaf treatment in a treatment performed can be before and after the germination of the leaves.

Particularly named harmful weeds that can be effectively controlled by herbicides according to the invention are: 5 Johnson grass, duck grass, para grass, "southern sandbar", finger grass, beremma grass, crowfoot grass, large wild apple grass , wild apple grass, barnyard grass, bush rice, loosestrife grass, goose grass, "cogon" grass, wrinkle grass, southern cut grass, "bearded splangle top", red "splangle top", Mexican "splangle top", brown " top panicum ", sour paspalum, water-paspalum, young grass, 10" raoul "grass, green foxtail, bushy foxtail, yellow foxtail.

The new compounds according to the invention have a low vapor pressure and no phytotoxic influence on the growth of grassy plants such as wheat, barley, oats and rye.

The pyridyloxyphenoxy unsaturated derivatives of formula 1 can be prepared by performing the methods listed below.

The pyridyloxyphenoxy unsaturated derivatives of formula 1, wherein Z has the same meaning as indicated above, can be prepared by reacting an unsaturated halide of formula 2 with a pyridyloxy phenol of formula 3, indicated on the formula sheet, in the presence of a base at a temperature of 0-150 ° C for 1-20 hours and optionally converting Z 'to Z. The meaning of Z' and Z 'and Hal are the same as indicated above. In the formulas, the groups convertible to Z include cyano, haolgene and other functional groups.

Suitable bases include alkali metal hydroxides such as sodium hydroxide or potassium hydroxide, alkali metal carbonates such as sodium carbonate, potassium carbonate, sodium bicarbonate, alcoholates such as sodium ethylate and tertiary amines such as triethylamine, dimethylaniline or pyridine.

Suitable reaction media include water, acetone, methyl ethyl ketone, methanol, isopropanol, butanol, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, benzene, toluene, xylene, chlorobenzene, chloroform, carbon tetrachloride, dichloroethane and the like.

The resulting compound can be converted into a desired pyridyloxyphenoxy unsaturated derivative by following the following procedure.

The desired compound of the pyridyloxyphenoxy unsaturated derivatives of formula 1, indicated on the formula sheet, can be obtained by a 790 4 2 42 tpr * "-a * - *" -% 4 -4-20676 / Vk / iv

direct reaction of a pyridyloxyphenol of formula 10, shown on the formula sheet, with a halopentene compound or a halopentenol compound of formula Hal-CHCH = CH2

ch3 in the presence of base in a suitable solvent at a temperature of 0-150 ° C for 1-20 hours.

i

The desired compounds of the pyridyloxyphenoxy unsaturated acid esters of formula 11, indicated on the formula sheet, can be prepared by effecting a reaction between the pyridyloxyphenol of formula 10 indicated. on the formula sheet, with a halopenentenic acid to prepare a pyridyloxyphenoxy unsaturated acid of formula IV, indicated on the formula sheet, and then reacting the corresponding compound of formula ROH with the pyridyloxyphenoxy unsaturated acid of formula 4 or the acid halide with formula 9, indicated on the formula sheet, in a suitable solvent, or 15 without solvent at a temperature of 0-150 ° C for 1-20 hours.

The pyridyloxyphenoxy unsaturated acid halide of formula 9 can be easily obtained by reacting a halogenating agent such as thionyl chloride and phosphorus trihalides with the pyridyloxyphenoxy unsaturated acid of formula 4 indicated on the formula sheet.

The desired compounds of the esters of the pyridyloxyphenoxy unsaturated acid of formula 12 can also be obtained by reacting the pyridyloxyphenoxy unsaturated acids of formula 4 or the acid halide thereof of formula 9 with the corresponding mercaptan in the presence of a base as a hydrogen halide extracting agent in a suitable inert solvent or without solvent at a temperature of -10 to 150 ° C for 1-20 hours.

The desired compounds of the pyridyloxyphenoxypentenols of formula 13, indicated on the formula sheet, can be prepared by hydrogenating the pyridyloxyphenoxy unsaturated acid of formula 4 or its acid halide of formula 9 or its ester, with a reducing agent such as sodium borohydride and lithium aluminum hydride in a suitable inert solvent at a temperature between -20 ° C and 100 ° C for 1-20 hours.

The desired compounds can also be prepared by effecting the reaction between the pyridyloxyphenol of formula 3, with the unsaturated halide of formula 2 and, if necessary, converting the product to 7904242 L -5-20676 / Vk / iv c * - ..

desired connection.

Also listed below are some methods for converting the product obtained by the main reaction.

a) The pyridyloxyphenoxy, unsaturated derivatives of formula 1, indicated 5 on the formula sheet, can be prepared by reacting a pyridyloxyphenoxy unsaturated acid of formula 4, indicated on the formula sheet, with a compound of formula ROH, where R has the same meaning as above is given in the presence of a catalyst such as an aromatic sulfonic acid, especially benzenesulfonic acid, toluenesulfonic acid or phenaphthalenesulfonic acid, an anhydrous sulfate such as anhydrous copper sulfate or anhydrous iron sulfate, phosphorus oxychloride, phosphoric anhydride, boron trifluoride or an acid ion exchanger at a temperature of 20 150 ° C or under reflux for 1-20 hours.

b) The pyridyloxyphenoxy unsaturated derivatives of formula 1, indicated on the formula sheet, can be prepared by a reaction between a pyridyloxyphenoxy unsaturated acid of formula 4, indicated on the formula sheet, with a base such as alkali metal hydroxide, alkaline earth metal hydroxide and organic bases especially amines and amino compounds in a reaction medium at a temperature of 0-100 ° C for 0.5-10 hours.

C) the pyridyloxyphenoxy unsaturated derivative of the formula 1, indicated on the formula sheet, can be prepared by a reaction between the pyridylphenoxy-pentenoylhalide of the formula 5, indicated on the formula sheet, with a compound of formula ROH, R'SH, wherein R and R 'have the same meaning as indicated above, in the presence of a hydrogen halide extracting agent such as a base, in a reaction medium or excess of the compound of formula ROH or without a reaction medium at a temperature between -10 ° C and 150 ° C for 1-20 hours.

Suitable inorganic or organic base hydrogen halide extractants are alkali metal hydroxides, especially sodium hydroxide or potassium hydroxide, alkali metal carbonates such as sodium carbonate, potassium carbonate, or sodium bicarbonate, alcoholates such as sodium ethyline, and tertiary amines such as triethylamine, dimethyl amine.

Suitable reaction media include acetone, methyl ethyl ketone, dimethyl formamide, dimethyl sulfoxide, tetrahydrofuran, benzene, toluene, xylene, chloro-benzene, chloroform, carbon tetrachloride and dichloroethane.

7904242 ''%. :? ; · '. -6- 20676 / Vk / iv

The pyridyloxyphenoxypentene halide of formula 5> indicated on the formula sheet, can be prepared by reacting the pyridyloxyphenoxy unsaturated acid of formula 4, indicated on the formula sheet, and thionyl chloride or phosphorus trihalide in a solvent * d) The pyridyloxyphenoxy pentenoate of formula 6, indicated on the formula sheet, wherein M is an alkali metal, an alkaline earth metal, a heavy metal or an amino group, especially alkylamino and an arylaraino group, can be readily prepared by neutralizing the corresponding acid or acid content with the corresponding base. The reaction is preferably conducted in a solvent at a temperature above room temperature.

e) The pyridyloxyphenoxypentenol derivatives of formula 7, indicated on the formula sheet, wherein B represents a hydrogen atom, an alkylcarbonyl * a haloalkylcarbonyl, an arylcarbonyl, an alkylaminocarbonyl or an arylaminocarbonyl group, can be readily prepared by effecting a reaction between 4-halogen 2-pentanol or its ester, with a pyridyloxyphenol of formula 3, indicated on the formula sheet. The reaction is preferably carried out in a solvent in the presence of a base. When the pyridyloxyphenoxy-pentenol (B = H) is prepared, the product can be esterified to yield the corresponding ester.

f) The pyridyloxyphenoxypéntenols of formula 8, indicated on the formula sheet, can be prepared by a pyridyloxyphenoxy unsaturated derivative of formula 14, indicated on the formula sheet, wherein A 'is OR or a halogen atom obtained by using the process a ) ,. b), c), d) or e) in the presence of a reducing agent such as lithium aluminum hydride and sodium borohydride in a reaction medium at a temperature between -20 ° C and 100 ° C for 1-20 hours.

If necessary, the resulting pyridyloxyphenoxypentenol is esterified with the corresponding acid to obtain the ester.

The invention is further elucidated by means of the following examples, in which the preparation of certain compounds within the scope of the invention is indicated.

Example I

The preparation of methyl 4- [4- (3,5-dichloropyrid-2-yloxy) phenoxy] - (2) -pentenoate.

In a solution of .12.8 g (0.05 mol) 4- (3,5-dichloropyrid-2-yloxy) phenol 7904242 v cti-7- 20676 / Vk / iv t f; and 11.6 g (0.06 mol) of methyl 1-4-bromo (2) -pentenoate in 70 ml of methanol were fed 7.6 g (0.055 mol) of potassium carbonate and the mixture was refluxed for 3 hours in the reaction to accomplish. The reaction mixture was extracted with diethyl ether and the ether phase was washed with water then with dilute hydrochloric acid then with water and dehydrated over anhydrous sodium sulfate and the ether was distilled off and the low boiling compounds were distilled off at a temperature of 140 ° C under a pressure of 0.01 mm of mercury to obtain 16.4 g of an orange viscous liquid with a refractive index is 1.5548. (Yield 89.2%).

Example II

The preparation of 4- [4- (3,5-dichloropyrid-2-yloxy) phenoxy] - (2) -pentenoic acid.

A solution of sodium ethylate was prepared by adding 0.9 g (0.04 mol) of sodium metal in 70 ml of ethanol and to this was added 9.0 g (0.035 mol) of 4- (3,5-dichloropyrid-2-yloxy) phenol and then 9.4 g (0.045 mole) of ethyl 4-bromo (2) -pentenoate. The mixture was refluxed for three hours to effect the reaction and 24 ml of 10% aqueous solution of sodium hydroxide was added to the mixture and the mixture was further refluxed for 30 minutes. The reaction mixture was poured into 150 ml of water to obtain a solution of 10 sodium 4- [4- (3,5-dichloro-pyrid-2-yloxy) phenoxy]) - (2) -pentenoate. Concentrated hydrochloric acid was added to the solution to effect acidic conditions, whereby an oily product was formed and solidified. The solid product was filtered and dried and recrystallized from ethanol to obtain 9.7 g of white powdery crystals, corresponding to a yield of 78.3%, which has a melting point of 157-159 ° C.

Example III

The preparation of sodium 4- [4- (3,5-dichloropyrid-2-yloxy) phenoxy] (2) pentenoate.

50 17.7 g (0.05 mol) 4- [4- (3,5-dichloropyrid-2-yloxy) phenoxy] - (2) -pentenoic acid was dissolved in 24.1 g (0.05 mol) 5 % aqueous solution of sodium hydroxide and then water was distilled off to obtain 180 g (yield 95.5%) of white, powdery crystals, mp 240-245 ° C.

jg According to the same procedure, the potassium salt can be obtained under 7904242 «· * -.- ·. · ... · - \ '; ·.

-8-. 20676 / Vk / iv using potassium hydroxide. The calcium, iron, zinc, magnesium, manganese or aluminum salt can be obtained by reacting the corresponding metal salt with an aqueous solution of the sodium salt or the potassium salt.

Example IV

. The preparation of 4- [4- (3,5-dichloropyrid-2-yloxy) phenoxy} - (2) -pentenoic acid dimethylamine salt.

14.2 g (0.04 mol) of 4- [4- (3,5-dichloropyrid-2-yloxy) phenoxy] (2) -pentenoic acid were dissolved in 30 ml of 5% aqueous solution of dimethylamine and then the excess dimethylamine and water were distilled off using a rotary evaporator to obtain 15.6 g of an orange viscous liquid, corresponding to a yield of 97> 4%. >

According to the same procedure, the ammonium salt, methyl amine salt, ethyl amine salt, n-propylamine salt, isopropylamine salt, diethylamine salt, di-n-15 propylamine salt, di-isopropylamine salt, dibutyl amine salt, triethyl amine pyridine salt, and picolinyl salt. -dichloropyrid-2-yloxy) phenoxy] - (2) -pentenoic acid.

Example V

The preparation of ethyl 4- (3,5-dichloropyrid-2-yloxy) phenoxy (2) -20 pentenoate.

A mixture of 17.7 g (0.05 mol) of 4- (4- (3,5-dichloropyrid-2-yloxy) phenoxy] (2) -pentenoic acid, 50 ml of ethanol, 50 ml of benzene and 3 g of concentrated sulfuric acid was added refluxed for 4 hours including the water was removed by a distillation step. The reaction mixture was diluted with 100 ml of benzene and washed with water and the benzene phase was dehydrated over anhydrous sodium sulfate and the benzene was distilled off and low boiling. compounds were distilled off at 140 ° C under a reduced pressure of 0.01 mm of mercury to obtain 15.2 g of an orange viscous liquid with a refractive * 20 index ηβ of 1.5697, corresponding to a yield of 82.8% ..

Example VI

The preparation of sec-butyl-4- (4- (3,5-dichloropyrid-2-yloxy) phenoxy] (2) -pentenoate.

A mixture of 10.6 g (0.03 mol) of 4- [4- (3,5-dichloropyrid-2-yloxy) phenoxy] -2-pentenoic acid and 30 ml of thionyl chloride was refluxed for 6 hours to response. The excess thionyl 790 4 2 42 L -9-20676 / Vkr / iv chloride was distilled from the reaction mixture and the acid chloride residue was mixed with 30 ml sec-butanol. After the addition, the reaction mixture was gradually heated to effect the reaction at 60 ° C for 5 hours. The excess sec-butanol was distilled off to obtain 5. 10.7 g orange T viscous liquid, with a refractive index np of 1.5565, corresponding to a yield of 90.3%.

Example VII

The preparation of allyl-4- (4- (3,5-dicloro-pyrid-2-yloxy) phenoxy] - (2) -pentenoate.

0 11.2 g (0.03 mol) 4- [4- (3,5-dichloropyrid-2-yloxy) -phenoxy] - (2) -pentenoyl / chloride obtained according to example VI, was added to a mixture of 2.3 g (0.04 mol) of allyl alcohol, 2.6 g (0.033 mol) of pyridine and 100 ml of anhydrous toluene with stirring and cooling, and the mixture was stirred at room temperature for 3 hours. The product was washed with water and dehydrated over anhydrous sodium sulfate and toluene was distilled off and the low boiling substances were distilled off at a temperature of 140 ° C under reduced pressure, namely at 0.01 mm mercury to obtain 9.8 g of orange, viscous 20 liquid with a refractive index n ^ of 1.5706, which corresponds to a yield of 86.5%.

) By the same procedure except that 2-butenyl alcohol or 1-butynyl alcohol

alcohol was used instead of allyl alcohol, esterification was carried out to obtain butenyl-4- [4- (3,5-dichloropyrid-2-yloxy) -phenoxy] - (2) -pentenoate and butynyl 4- [4- (3 5-dichloropyrid-2-yloxy) -phenoxy] (2) -pentenoate. Example VIII

> The preparation of methoxyethoxyethyl-1-4- (3,5-dichloropyrid-2-yloxy) -phenoxy] - (2) -pentenoate.

A mixture of 35.5 g (0.1 mol) 4- (4- (3,5-dichloropyrid-2-yloxy) phenoxy] (2) -pentenoic acid, 24 g (0.2 mol) 2- (2- methoxyethoxy) ethanol, 100 ml of benzene and 5 g of concentrated sulfuric acid were refluxed for 7.5 hours until the distillation of water was finished. After the reaction, the benzene phase was washed with water and then with a 5% aqueous solution of sodium bicarbonate and finally with water and dehydrated over anhydrous sodium sulfate and the benzene distilled off as well as the low boiling substances at a temperature of 120 ° C under a reduced pressure of 0.06 mm mercury to obtain 38.6 g of orange, yellow, viscous liquid with a refractive 7904242 i. s * '*' · '·' -; -10-20676 / Vk / iv 20 index of 1.5685, which corresponds to a yield of 84.5%.

By following this procedure except that 2- (2-ethoxyethoxy) ethanol or 2- (2-n-propoxyethoxy) ethanol was used instead of 2- (2-methoxyethoxy) ethanol, esterification was accomplished to obtain ethoxyethoxy-5 methyl 4- [4- (3,5-dichloropyrid-2-yloxy) phenoxy]] - (2) -pentenoate or n-propoxyethoxyethyl-4 - [_ 4- (3,5-dichloropyrid-2- yloxy) phenoxy (2) -pen tenoate.

Example IX.

The preparation of pyridylmethyl-4- [4- (3,5-dichloropyrid-2-yloxy) phenoxy] - (2) -pentenoate.

A mixture of 11.2 g (0.03 mol 4- [4- (3,5-dichloropyrid-2-yloxy) phenoxy] - (2) -pentenoyl chloride and 7.1 g (0.065 mol) 3-hydroxymethylpyridine in 50 ml of benzene was heated with stirring for 4 hours After the reaction, the reaction mixture was cooled and washed successively with water, with a 5% aqueous solution of sodium bicarbonate with water, with 5% hydrochloric acid and with water and then dehydrated over anhydrous magnesium sulfate and the benzene was distilled off to obtain 12 g of red-brown viscous liquid 20

with a refractive index / n var 1.5670, which corresponds to a yield of 92.3%. D

According to the same method, except that benzyl alcohol was used instead of 3-hydroxymethylpyridine, the esterification was carried out to obtain benzyl-4- [4- (3,5-dichloropyrid-2-yloxy) phenoxy) (2) -pentenoate.

Example X.

The preparation of 3-methoxy-3-methylbutyl-4- {4- (3,5-dichloropyrid-2-yloxy) phenoxy] - (2) -pentenoate.

5.1 g (0.02 mole) of 4- (3,5-dichloropyrid-2-yloxy) phenol and 6.1 g (0.022 mole) of 3-methoxy-3-methylbutyl-4-bromine were added in 50 ml of methyl ethyl ketone -2-pentenoate dissolved and 3.0 g (0.022 mol) of sodium carbonate were added to the solution at room temperature with stirring. The mixture was refluxed for 5 hours. After cooling, it was filtered and 200 ml> 30 benzene added to the filtrate and washed with 50 ml saturated aqueous sodium bicarbonate solution, this operation was performed twice and then 50 ml was added which was repeated twice, and dehydrated over anhydrous sodium sulfate and the benzene was distilled off and the low boiling substances were distilled off at 105 ° C under a reduced pressure of 0.12 mm of mercury to obtain 8.1 g of light brown, viscous liquid 7904242 t-20-11. 20676 / Vk / iv fabric with a refractive index n ^ of 1.5547. The yield corresponds to 89.1%. Following the same procedure except that 3-ethoxy-3-methyl-butyl-4-bromo-2-pentenoate was used instead of 3-methoxy-3-methyl-butyl- 4-Bromo (2) -pentenoate, the synthesis was accomplished to obtain 5 3-ethoxy-3-methylbutyl-4- {4- (3,5-dichloropyrid-2-yloxy) phenoxy] - (2) -pentenoate.

Example XI

The preparation of S-methyl-4-yf- (3,5-dichloropyrid-2-yloxy) phenoxy] - (2) -pentethiolate.

2.9 g (0.06 mol) of methyl mercaptan and 7.6 g (0.055 mol) of potassium carbonate were dissolved in 100 ml of toluene and 20.5 g (0.05 mol) of 4- (4- (3,5-dichloropyrid) 2-yloxy) phenoxyl- (2) -pentenoyl bromide was added to the solution at 5-10 ° C with stirring to react the mixture at room temperature for 4 hours Water was added to the reaction mixture and the toluene phase was washed with water and dehydrated over anhydrous sodium sulfate and 15 toluene was distilled off to obtain 16.7 g of an orange viscous liquid with a refractive index of 1.6072, corresponding to a yield of 86.9%.

By performing the same procedure except that ethyl mercaptan, propyl mercaptan or butyl mercaptan was used instead of methyl mercaptan, S-ethyl, S-propyl or S-butyl 4- [4- (3,5-dichloropyrid-2-yloxy) f enoxy] - (2) -pentethiolate.

Example XII

The preparation of 4- / 4- (3,5-dichloropyrid-2-yloxy) phenoxy] - (2) -penten-1-ol. 150 ml diethyl ether was suspended in suspension 0.9 g (0.0226 mol) lithium aluminum hydride and then a solution of 8.4 g (0.0226 mol) 4-4- (3,5-dichloropyrid-2-yloxy) phenoxy } - (2) -pentenoyl chloride in 50 ml diethyl ether added dropwise to the suspension at a temperature of 10-15 ° C for 30 minutes. After the addition, the mixture was stirred at room temperature for 1 hour to effect the reaction and the reaction mixture was poured into 100 ml of ice water and the ether phase was washed with water and dehydrated over anhydrous sodium sulfate and ether was distilled off to give 6.0 g orange, yellow, viscous liquid with a refractive index on Πρ of 1.5784, which corresponds to a yield of 77.9%.

790 4 2 42 '-.

-12- 20676 / Vk / iv

Example XIII

The preparation of 2-chloroethyl-4 -4-(3,5-dichloropyrid-2-yloxy) phenoxyl (2) -pentenoate.

5.6 g (0.015 mol) of 4- (4-dichloropyrid-2-yloxy) 5-phenoxy] (2) -pentenoyl chloride and 1.3 g (0.017 mol) of ethylene chlorhydrin were mixed in 50 ml of benzene. and the mixture was refluxed for 3 hours until development of hydrogen chloride had stopped. After cooling, the reaction mixture was washed with a 5% aqueous solution of sodium hydroxide and then with water. The benzene layer was dehydrated over anhydrous sodium sulfate and benzene was distilled and low boiling compounds were distilled off under reduced pressure at 110 ° C at a pressure of 0.07 mm of mercury to obtain 5.2 g of an orange viscous liquid with a refractive index of 1.5770, which corresponds to a yield of 83.2%.

By performing the same procedure except that ethylene bromohydridine, 2,2,2-trichloroethyl alcohol or 3-chloropropyl alcohol was used instead of ethylene chlorohydrin, the synthesis was carried out to obtain 2-bromoethyl, 2,2,2-trichlorethyl or 3 chloropropyl-4- (4- (3,5-dichloro-pyridin-2-yloxy) phenoxy] (2) -pentenoate.

Example XIV

The preparation of p-tolyl-4- [4- (3,5-dichloropyrid-2-yloxy) phenoxy] (2) pentenoate.

5.6 g (0.015 mol) of 4- [4- (3,5-dichloropyrid-2-yloxy) phenoxy] - (2 -) - pentenoyl chloride were dissolved in 20 ml of acetone. The solution was added dropwise to a solution of 1.6 g (0.015 mole) of 4-methylphenol and 1.3 g (0.15 mole) of sodium bicarbonate in 20 ml of acetone at 10-15 ° C with cooling for 10 minutes. After the addition, the reaction mixture was stirred at room temperature for 1 hour and then poured into water. The oily product obtained was extracted with benzene.

The benzene layer was washed with a 5% aqueous solution of sodium hydroxide, then with water and dehydrated over anhydrous sodium sulfate, and the benzene was distilled off and the low boiling compounds were distilled off under reduced pressure at 100 ° C and a pressure of 0.08 mm of mercury to obtain 5.8 g of a brown viscous liquid with a refractive index 20 rip of 1.5699. This corresponds to a yield of 86.5%.

By using the same method except that phenol, 3-methyl-790 4 2 42 -13- 20676 / Vk / iv.

* * * phenol, 4-chlorophenol was used instead of 4-methylphenol, the synthesis was repeated to obtain phenyl, 3-methylphenyl or 4-chlorophenyl-4- ^ 4- (3,5-dichloropyrid-2-yloxy) phenoxy] - (2) -pentenoate.

Specifically named compounds obtained by the method according to the invention will be indicated below. The compounds are indicated by numbers and these have also been used in the further course of the description.

Compound 1 4- [4- (3,5-dichloropyrid-2-yloxy) phenoxy] - C2) pentenoic acid 10 white powder crystalline melting point 157-159 ° C Compound 2

sodium 4- [4- (3,5-dichloropyrid-2-yloxy) phenoxy] - (2) -pentenoate white powder crystal form 15 melting point 241-245 ° C

Compound 3 4- [4- (3,5-dichloropyrid-2-yloxy) phenoxy] - (2) -pentenoic acid diethylamine salt orange, viscous liquid Compound 4 20 methyl-4- {4- (3,5-dichloropyrid-2-yloxy) ) phenoxy] - (2) -pentenoate orange, viscous liquid 20 refractive index n ^ of 1.5548 boiling point> 130 ° C at a pressure of 0.01 mm mercury

Compound 5 ethyl-4-j4- (3,5-dichloropyrid-2-yloxy) phenoxy] - (2) -pentenoate orange, viscous liquid 20 * refractive index n ^ of 1.5697 * boiling point ^ 135 ° C at a pressure of 0.07 mm mercury

Compound 6 50 n-propyl-4- (4- (3,5-dichloropyrid-2-yloxy) phenoxy] - (2) -pentenoate orange, viscous liquid refractive index of 1.5614 boiling point> 120 ° C at a pressure of 0.1 mm mercury 7904242 - 14- 20676 / Vk / iv «- ''

Compound 7 isopropyl-4-yf- (3,5-dichloropyrid-2-yloxy) phenoxy) - (2) -pentenoate orange, viscous liquid refractive index n ^ of 1.5593, boiling point> 130 ° C at a pressure of 0.01 mm mercury * Compound 8 sec-butyl-4-] 4- (3,5-dichloropyrid-2-yloxy) phenoxy (2) -pentenoate orange, viscous liquid 20 refractive index nQ of 1.5565 10 boiling point> 120 ° C at a pressure of 0.2 ram mercury

Compound 9 2-chloroethyl-4- [4- (3,5-dichloropyrid-2-yloxy) phenoxy] (2) pentenoate orange, viscous liquid 20 refractive index vanρ of 1.5770 15 boiling point ^> 110 ° C at a pressure of 0.07 mm mercury

Compound 10 2-Bromoethyl-4- (t- (3,5-dichloropyrid-2-yloxy) phenoxy] (2) -pentenoate orange, viscous liquid refractive index n of 1.5810, boiling point 125 ° C at a pressure of 0.1 rara mercury

Compound 11 allyl-4- [4- (3,5-dichloropyrid-2-yloxy) phenoxy] (2) -pentenoate orange, viscous liquid 20 refractive index n ^ of 1.5706 boiling point> 120 ° C at a pressure of 0.1 rara mercury

Compound 12 propargyl-4 - & - (3,5-dichloropyrid-2-yloxy) phenoxy (2) -pentenoate orange, viscous liquid 20 refractive index n ^ of 1.5905, boiling point> 130 ° C at a pressure of 0 .06 rara mercury

Compound 13 phenyl-4- [4- (3,5-dichloropyrid-2-yloxy J phenoxy] (2) -pentenoate orange, viscous liquid 20 refractive index n ^ of 1.5601 boiling point> 110 ° C at a pressure from 0> 07 mm mercury 790 4 2 42 -15- 20676 / Vk / iv HÈ * t

Compound 14 methoxyethoxyethyl-4-04- (3,5-dichloropyrid-2-yloxy) phenoxy ^ - (2) pentenoate brown viscous liquid 20 refractive index rip of 1.5685 boiling point> 125 ° C at a pressure of 0, 07 mm mercury

Compound 15 pyridylmethyl-4- [4- (3,5-dichloropyrid-2-yloxy) phenoxy] (2} -pentenoate) brown, viscous liquid, refractive index n, 1.5670, boiling point 110 ° C at a pressure of 0 .7 mm mercury

Compound 16 p-tolyl ^ 4- [4- (3,5-dichloropyrid-2-yloxy) phenoxy] (2) -pentenoate brown viscous liquid 20 refractive index n ^ of 1.5699 I boiling point> 100 ° C at a pressure of 0.08 mm of mercury

Compound 17 3-methoxy-3-methylbutyl-4- [4- (3,5-dichloropyrid-2-yloxy) phenoxy] (2) -t pentenoate light brown, viscous liquid 20.0 refractive index n <1.5547 boiling point> 110 ° C at a pressure of 0.1 mm mercury Compound 18 S-methyl-4- [4- (3,5-dichloropyrid-2-yloxy) phenoxy] (2) pentethiolate brown p, viscous liquid refractive index n ^ from 1,6072

Compound 19 S-ethyl-4-fe- (3,5-dichloropyrid-2-yloxyphenoxy) (2) -pentethiolate brown viscous liquid 20 refractive index nD of 1.5973 0 Compound 20 Sn-propyl-4- ^ 4- ( 3,5-dichloropyrid-2-yloxy) phenoxy- (2) -pentethiolate brown viscous liquid 20 refractive index nD of 1.6002 boiling point> 125 ° C at a pressure of 0.04 mm mercury 7904242-166767 / Uk / iv. .- «-V.

Compound 21 Sn-butyl-4- (4- (3,5-dichloropyrid-2-yloxy) phenoxy] (2) -pentethiolate brown, viscous liquid 20 'refractive index of ΐ6ΐ20 5 boiling point> 120 ° C at a pressure of 0.03 mm mercury

Compound 22 4- (3,5-dichloropyrid-2-yloxy) phenoxy- (2) -penten-1-ol orange-yellow viscous liquid refractive index of 1.5784.

The new compounds of the invention prepared by the above synthesis have significant herbicidal influences and no phytotoxic effect compared to many plants to be harvested and can be applied to the land, garden, fruit trees, forests and non-cultivation soils by carrying out a soil treatment or by a leaf treatment by a choice of the appropriate method} by the application and the appropriate dosage of the active ingredient.

The dosage of the active component of the composition according to the invention depends on the weather conditions, the composition of the soil, the form of the composition, the season in which the composition is applied and the method of administration and the type of plant to be harvested. and the weed species and the growth stage of the weeds but is usually 0.01 to 10 kg, preferably 0.1 to 5 kg, in particular 0.5 to 3 kg per hectare in the soil treatment or the leaf treatment and is usually used at a concentration of 10 to 10000 ppm, preferably 100 to 5000 ppm, in particular 250 to 3000 ppm of active substance. When applying the herbicidal composition by spraying it from an airplane, the concentration of active substance is usually 10,000 to 75,000 ppm. For example, 0.5 to 1.5 kg of active substance are sprayed in an amount of 20 to 50 l / ha. When the compound of the invention is used as a herbicide, the compound can be used in the original form and in the form of certain compositions such as granules, wettable powder, dust, emulsifiable concentrate, fine powder, light-buoyant, suspension and the like. to ensure proper functioning.

In the preparation of the herbicidal composition, the compound 35 according to the invention is uniformly mixed with or dissolved in suitable additives such as a solid carrier, especially talc 790 4 2 4 2 I -Λ · - - 17-20676 / Vk / iv , bentonite, clay, kaolin, diatomaceous earth, silica gel, vermiculite, lime, silicon-containing sand, ammonium sulfate or nreum, liquid carriers such as alcohols, dioxane, acetone, cyclohexanone, methylnaphthalene or dimethylformamide, surfactants such as 5 emulsifiers or dispersants or wetting agents such as alkyl sulfate, alkyl sulfonate, polyoxyethylene glycol ethers, polyoxyethylene alkyl aryl ethers such as polyoxyethylene nonyl phenol ether or polyoxyethylene sorbitan monoalkylate and carboxymethyl cellulose, gum arabic and other auxiliaries *

The amounts of active substance, additives and excipients in the herbicidal composition according to the invention will be explained in more detail below.

Wettable powder:> active substance 5-95 wt.%, Preferably 20-50 wt.% Surfactant 1-20 wt.%, Preferably 5-10 wt.% Solid support 5-85 wt.%, At preferably 40-70 wt%.

The active substance is mixed with the solid carrier and the surfactant and the mixture is crushed.

Emulsifiable concentrate: active substance 5-95 wt.%, Preferably 20-70 wt.% 20 surfactant 1-40 wt.%, Preferably 5-20 wt.% Liquid carrier 5-90 wt.%, Preferably 30-60 wt%.

The active substance is dissolved in the liquid carrier and the surfactant is mixed with it.

Dusty preparation: 25 active substance. 0.5-10 wt%, preferably 1-5 wt%, solid drier 99.5-90 wt%, preferably 99-95 wt%.

The active substance is mixed with a finely divided solid carrier, and the mixture is crushed.

Granular composition: active substance 0.5-40 wt.%, Preferably 2-10 wt.% Solid support, 99.5-60 wt.%, Preferably 98-90 wt.%.

The active substance is sprayed on the solid support or formed on the solid support as a coating to obtain granules.

Other herbicides may also be incorporated into the herbicidal composition of the invention.

7904242

ν '; . * V

-18- 2067 (5VVk / iv

Suitable other herbicides are: compounds of the carboxylic acid type such as 2,3,6-trichlorobenzoic acid and its salts, 2.3.5.6 tetrachlorobenzoic acid and its salts, 2-methoxy-3,5,6-trichlorobenzoic acid and its salts, 2-methoxy -3,6-dichlorobenzoic acid and its salts, 2-methyl-3,6-dichlorobenzoic acid and its salts, 2,3-dichloro-6-methylbenzoic acid and its salts, 2,4-dichlorophenoxyacetic acid and its salts and esters, 2,4,5 -trichlorophenoxyacetic acid and its salts and esters, 2-methyl-4-chlorophenoxyacetic acid and its salts and esters, 2- (2,4,5-trichlorophenoxy) propionic acid and its salts and esters, 4- (2,4-dichlorophenoxy) butyric acid and its salts and esters, 4- (2-methyl-4-chlorophenoxy) butyric acid and its salts and esters, 2,3,6-trichlorophenylacetic acid and its salts, 3,6-endoxohexahydrophthalate and its salts, dimethyl-2,3, 5,6-tetrachloroterephthalate, trichloroacetic acid and its salts, 2,2-dichloropropionic acid and its salts and 2,3-di chloroisobutyric acid and its salts, carbamic acid herbicides such as 5-ethyl-N, N-di (n-propyl) thiol carbamate, S-n-propyl-N, N-di (n-propyl) thiol carbamate, ·.

S-ethyl-N-ethyl-N- (n-butyl) thiol carbamate, 25 Sn-propyl-N-ethyl-M- (n-butyl thiol carbamate, S-2-chloroallyl-IT, M-diethyldithiocarbamate, N-methyl dithiocarbamate , S-ethyl-hexahydro-1H-azepine-1-carbothioate, S- (4-chlorobenzyl) -N, N-diethylthiol carbamate, S-benzyl-N, N-di-sec-butyl-thiol carbamate, isopropyl-N- phenyl carbamate, isopropyl N- (3-chlorophenyl) carbamate, 4-chloro-butyn-2-yl-N- (3-chlorophenyl) carbamate, methyl N- (3,4-dichlorophenyl) carbamate and 35 methyl N- (4-aminobenzenesulfonyl) carbamate, 790 4 2 42 -19- 20676 / Vk / iv I phenol herbicides, in particular 2-sec-butyl-4,6-dinitrophenol and its salts, and pentachlorophenol and salts of these, urea-type herbicides, in particular 5- (3,4-dichlorophenyl) -1,1-dimethylurea, 3-phenyl-1,1-dimethylurea, 3- (3,4-dichlorophenyl) -3- methoxy-1,1-dimethylurea, 3- (4-chlorophenyl) -3-methoxy-1,1-dimethylurea, 3- (3,4-dichlorophenyl} -1-n-butyl-1-methylurea, 10 3- ( 3,4-dichlorophenyl-1-methoxy-1-methyl urea, 3- (4-chlorophenyl) -1-methoxy- 1-methyl urea, 3- (3,4-dichlorophenyl) -1,1,3-trimethyl urea,> 3- (3,4-dichlorophenyl) -T, 1-diethyl urea, 1 - (2-methylcyclohexyl) -3 phenyl urea, 15 1- (5-t-butyl-1,3,4-triadiazol-2-yl) -1,3-dimethyl urea, 3- (3-chloro-4-methylphenyl) -1,1- dimethyl urea, 3- (3-chloro-4-methoxyphenyl) -1,1-dimethyl urea and dichloro-urea, herbicides of the triazine type such as 20 2-chloro-4,6-bis (ethylamino) -s-triazine, 2-chloro 4-ethylamino-6-isopropyl-amino-s-triazine, 2-chloro-4,6-bis (methoxypropylamino) -s-triazine, 2-methoxy-4,6-bis (isopropylamino) -s-triazine ,.

2-methylmercapto-4,6-bis (isopropylamino) -s-triazine, 2-methylmercapto-4,6-bis (ethylamino) -s-triazine, 2-methylmercapto-4-ethylamino-6-isopropylamino-s-triazine , 2-chloro-4,6-bis (isopropylamino) -s-triazine, 2-methoxy-4,6-bis (ethylamino) -s-triazine, 2-methoxy-4-ethylamino-6-isopropylamino-s-triazine 2-methyl-mercapto-4- (2-methoxyethylamino) -6-isopropylamino-s-triazine, 2- (2-chloro-4-ethylamino-s-triazin-6-yl) -amino-2-methyl-propionitrile, 4-amino-6-t-butyl-3-methylthio-1,2,4-triazine-5- (4H) -one and 3-cyclohexyl-6-dimethylamino-1-methyl-s-triazine-2,4- (1Η, 3H) dione, ether-type herbicides such as 2,4-dichloro-41-nitrodephenyl ether, 790 4242: -. '·' · - ·. ·.

-20- 20676 / Vk / iv 2,4,6-trichloro-4-nitrodiphenyl ether, 2,4-dichloro-6-fluoro-41-nitrodiphenyl ether, 3-methyl-4-nitrodiphenyl ether, 3,5-dimethyl-4 »- nitrodiphenyl ether,. · · * Λ.

5 2,4'-Dinitro-4-trifluomethyl-diphenyl ether, 2,4-dichloro-3r-methoxy-4'-nitrodif enyl ether, 2-chloro-4-trifluoromethyl-4'-nitrodif enyl ether, 2-chloro-4-trifluomethyl -3 '-ethoxy-4' -nitrodiphenyl ether, 2-chloro-4-trifluoromethyl-3 '-ethoxycarbonyl-4' -nitrodiphenyl ether and 10 2-chloro-4-trifluoromethyl-3 '-ethoxycarbonylethoxy-4 * -nitrodiphenyl ether, herbicides of the anilide type such as N- (3,4-dichlorophenyl) propionamide, N- (3,4-dichlorophenyl) -2-methyl acrylamide, N- (3-chloro-4-methyl-phenyl) -2-raethylpentamide, 15 N- (3,4-dichlorophenyl) -trimethylacetamide, N- (3,4-dichlorophenyl) -2,2-dimethylvaleramide. N-isopropyl-N-phenylchloroacetaraide, Nn-butoxymethyl-N- (2,6-diethylphenyl) chloroacetamide and Nn-methoxymethyl-N- (2,6-diethylphenyl) chloroacetamide, uricil type herbicides, especially compounds such as 5-bromo-3-sec-butyl-6-methyluracil, 5-bromo-3-cyclohexyl-1,6-dimethyluracil, 3-cyclohexyl-5,6-trimethylene uracil, 5-bromo-3-isopropyl-6-methyluracil and 25 $ 3-tert-butyl-5-chloro-6-methyluracil, nitrile-type herbicides such as 2,6-dichlorobenzonitrile, diphenylacetonitrile, 3,5-dibroam-4-hydroxybenzonitrile and 3,5-diiodo-4-hydroxybenzonitrile, and other herbicides such as 2-chloro-NjN-diallylacetamide, N- (1,1-dimethyl-propynyl) -3,5-dichlorobenzamide, maleelhydrazide, 3-amino-1,2,4-triazole, 7904242 * * »- 21- 20676 / Vk / iv r mono-sodium methane arsonate, di-sodium methane arsonate, N, N-dimethyl-2,2-diphenylacetamide, N, N-di (n-propyl) -2,6-dinitro-4-trifluoromethylaniline .5 N, N-di (n-propyl) -2,6-dinitro-4-methylaniline, N, N-di (n-propyl) -2,6-dinitro-4-methylsulfony laniline, 0- (2,4-dichlorophenyl) -O-methyl-N-isopropylphosphoramide fchioate, 4-amino-3,5,6-trichloropicolinic acid, 2,3-dichloro-1,4-naphthoquinone, 10 dimethoxythiocarbonyl disulfide, 3- isopropyl-1H-2,1,3-benzothiadiaziner4 (3H) -one-2,2-dioxide, 6,7-dihydrodipyrido [beta], 2-3: 2 *: 1 * -c] pyrazine salt, "1.1, - dimethyl-4,4'-bipyridine salt, 3,4,5'-6-tetrahydro-3,5-dimethyl-2H-1,3,5-thiadiazine-2-thione, 1,2-dimethyl-3,5- diphenylpyrazolain methylsulfate, N-sec-butyl-2,6-dinitro-3,4-xylidine, N-sec-bufcyl-4-t-butyl-2,6-dinitroaniline,, N-diethyl-2,4-dinitro -6-brifluoro-ethyl-1,3-phenylenediamine, 1,1,1-trifluoro (41-phenyl-sulfonyl) -methane-sulfono-O-toluidine, 20 2- (1-naphthoxy) -N, diethylpropionamide, 2 -t-bufcyl-4- (2,4-dichloro-5-isopropxyphenyl) -1,3,4-oxadiazole-2 (3H) on, 4-chloro-5-methylamino-2- («,« * , d-trifluoro-m-tolyl) Γ3 (2H) -pyridazinone, N-cyclopropylmethyl-d, d., A-trifluoro-2,6-dinitro-Hrpropyl-p-toluidine and N-phosphonmethylglycine.

When the other herbicide as mentioned above is mixed with the compound according to the invention, the ratio of the compounds and the dosage of the compounds depends on the selectivity and the herbicidal influence of the compounds on the plants to be harvested and the control of the noxious weeds that are treated with this.

Certain examples of preparations of the herbicidal composition will be explained below, in which the nature and ratio of the additives and auxiliary substances is not limited and can be varied as with conventional herbicidal compositions.

790 4 2 42 <r ~ 'v'. · ·· "-22- 20676 / Uk / iv

Composition 1; wettable powder.

Active 30 wt% sodium form of higher alcohol sulfate 5 wt% clay 65 wt% 5. These substances are mixed evenly and crushed to prepare a wettable powder.

Composition 2: emulsifiable concentrate.

active substance 25 wt.% polyoxyethylene alkylaryl ether 10 wt.% 10 calcium dinaphthylmethanesulfonate 5 wt.% xylene 60 wt.%

These compounds were mixed evenly to prepare an emulsifiable concentrate

Composition 3. · granules.

15 active substance 3 wt% bentonite 40 wt% clay 50 wt% sodium lignin sulfonate 7 wt%

These materials were mixed and crushed evenly, then kneaded with water and granulated and dried to give granules. Composition 4: substance-shaped preparation. active substance 2 wt.% clay. . 98 wt%

The materials were mixed and comminuted to prepare a substance-like composition.

Composition 5: wettable powder. active substance 30 wt.% kaolin 43 wt.% white carbon 20 wt.% 30 polyvinyl alcohol 5 wt.% polyoxyethylene nonylphenol 2 wt.%.

These materials were mixed evenly and comminuted to prepare a wettable powder.

35 7904242. -¾ ff 1 r -23- 20676 / Vk / iv

Composition 6: emulsifiable concentrate. " active substance 50 wt.% polyoxyethylene nonyl phenol 5 wt.% alkylarylsulfonate 5 wt.% 5 xylene 40 wt.%

These materials were mixed evenly to prepare an emulsifiable concentrate.

Composition 7: granules.

active substance 5 wt.% 10 siliceous sand 92 wt.% white carbon 3 wt.%

These materials were mixed evenly and the egg crushed then kneaded with water and granulated and dried to prepare granules. Composition 8: dusty preparation.

15 active substance 3 wt% white carbon - 2 wt% kaolin 95 wt%

These materials were mixed and crushed to prepare a dusty preparation.

20 7904242 I, <V:. .-.

a .

.1 -24- 20676 / Vk / tsΛι t

The herbicidal activity of the compound according to the invention will be further elucidated on the basis of the experiments carried out and the results thereof. In these experiments, the results are compared with the results obtained with compounds as shown on the formula sheet of formula 15-20.

EXPERIMENT I.

This test was performed on plants to be harvested and land-grown weeds at a pre-development stage by effecting a soil treatment.

For this purpose, each 600 cm pot was filled with soil from the land and seeds of wheat, barley, soybeans, radish, barnyard grass and tall crab grass, which seeds were applied at a depth of 0.5 cm. An emulsifiable concentrate was prepared according to the method indicated for composition 2 and it was diluted with water to obtain specific concentration of the component using one kiloliter / hectare and the diluted solution was sprayed evenly over the soil surface.

Twenty days after treatment, the herbicidal influence and phytotoxicity of the plants to be harvested was determined and the results were indicated as follows: HERBICIDAL INFLUENCE ON PHYTOTOXICITY: 10: Complete suppression of growth;

9: Growth suppression from 90 to 100 $; 8: Growth suppression from 80 to 90 $; 25 7: Growth suppression from 70 to 60 $; 6: Growth suppression from 60 to 50 $; 5: Growth suppression from 50 to 40 $; 4: Growth suppression from 40 to 50 $; 3: Growth suppression from 30 to 40 $; 30 2: Growth suppression from 20 to 30 $; 1: Growth suppression from 0 to 20 $; 0: No herbicidal influence.

The experiments were performed separately and the results of the 35 tests 1-1 to 1-5 are shown in Tables A, B, C, D and E respectively.

7904242 -25- 20676 / Vk / ts / ·· e * TABLE A (Test 1-1) 'Number of the ose beautification' ing ac- _; xgYg substance Ba. So. Ha. JB.G. Cr.G.

5 _Ckg / ha) _______ 1 0.5 '5 3 0 0 10 10 -__ 0.25 1 0__0 0 10 10 0.5 5 3 0 0 10 10 2 i 0.25 1 0 0 0 10 10 3 0.5 6 4 0 0 10 10 1Π 0.25 1 0 0 0 10 10 0.5 6 4 0 0 10 10 4 0.25 1 0 0 0 10 10 5; 0.5 5 4 0 0 10 10 I 0.25 20 0 0 10 10 "Ö75 5 i 0 δ Γ0 ΠΓ ~ b 0.25 1 0 0 0 10 10 15 ^ 0.5 '5 3 0 0 10 10 _____ 0.25 0 0 0 0 10 10 8 0.5 5 3 0 Q 10 ~ 10 0.25 0 0 0 0 10 10 9 ^ 0.5 "5 3 0 0 10 10 __0.25 0 0 0 (0 10 10 20 10 O 5 I η o I ίο io 0.25 0 0 0 0 10 10 O 5 5 ö Ö ΓΤ "To 11 0.25 0 0 0 0 10 10 J 0.5 6 4 Ö 0 10 * 10 12 _ 0.25 I 2 I 1 0 0 8 8 25 For comparison, please refer to the formula sheet with formula: '----- O 3 1 δ ö 5 δ 30 15 0.25 1 2 0 0 6 2 16 0.5 6 7 0 0 4 "" 5 __0.25 3 4__0__0__1 3 17 0.5 4 3 0 0 4 5 0.25 2 1 0 0 2 2 “'075 5 4 0 0 6 7 35.10 0.25 3. 2 0 0 3 4 0.5 7 7 0 0 5 6 _ ^ __ 0.25 I 3 1 4 1 0 1 0 1 2 1 3 790 4 2 42?. »5 r * '. ---- 1' 1

J

ί -26- 20676 / Vk / ts TABLE B (Test 1-2) 5 "Number of the Dosage compound active ingredient Wh. Ba. so. Ra. B.G. Cr.G.

^ _ (Kg / ha). _______ 13 Oi. 5 5 3 0 0 10 10 ___ 0.25 2__1__0 0__10 10 10 14 0.5 2 2 0 0 10 10 0.25 1 1 0 0 10 10 0.5 2 2 0 0 10 10 15 _I 0.25 1 1__0 0 10 10 16 0.5 2 2 0 0 10 10 __ 0.25 I 1 I 1 1 0 I 0 1 10 10 15 TABLE C (Test 1-3)

Number of the Dosage 20 compound active substance Wh. Ba. So. Ra> B.G. . Cr.G.

_, (Kg / ha) ____'_.__ 17 0.5 0 0 0 0 10 10

__0.25 I 0 1 0 0 10 10 IQ

25 TABLE D (Test 1-4)

Dosage number ^ ^ * ---- compound active substance Wh. Ba. So. Ra. B.G. Cr.G.

. (Kg / ha) ________; ____ ^ 0.5 0 0 0 0 10 10 - ____0. 25__0 0 0 0 10 10 35 0. 5 0 0 0 "* 0 '10 10 __. Q.25 1 0 10 0 1 0 10, 10, 7904242 -27- 20676 / Vk / ts <y? R

For comparison: compound dosage indicated - acfcive - on the for- Ba * So * Ra * B * u * br * u · 5 nuleblad dust j | t formu- (Kg / ha) '' __________ - 0.5 2 3 Ö 5 3 20 1 0.25 I 1 I 1 0 0 1 2. ..

10 TABLE E (Test 1-5) __ - _ _____

Number of the Dosage. . .. active _ _ Verbmdxng substance Wh. Ba. So. Ra. B.G. Cr.G.

__ (Kg / ha) ___. ____ 15 22 0.5 0 0 0 0 10 10 _ 0.25 0__0 0 1 0 I 10 1 10

Note:

Wh: Wheat Ba .: barley 2q So: Soybeans Ra .: radish B.G .: panicum crus-galli linnaeus Cr.O .: High Crab grass (digitaria sanguinalis scopoli).

EXPERIMENT II

These tests were performed against the plants and weeds to be harvested that appear on the land at a germination stage by treating the soil. To this end, a pot made of polyethylene 2 with a surface of 2000 cm was filled with soil and seeds of rice, tender, wheat, soybeans, cotton, radish, panicum crus-galli linnaeus, 30 digitaria sanguinalis scopoli, alopecurus aequalis sobolewki var were applied therein. amurensis ohwi, sorghum halepense and chenopodium album linnaeus var centrorubrum makino, 25 seeds of each plant were planted at a depth of 0.5 cm.

Each emulsifiable concentrate prepared according to the procedure indicated for composition 2 was diluted with water to obtain 0.25-0 / 125 and 0.0625 Kg / ha of active substance and the diluted solution was uniformly distilled 790 4 2 4 2 ^ Ψ c fc. - '* - - \ I' 28 ~ 20676 / Vk / ts $ * sprayed over the surface of the soil in the amount of 200 ml per pot.

Twenty days after treatment, the herbicidal influence and phyto-toxicity of the plants to be harvested were measured and the valuation was carried out as indicated in experiment I.

Tests 2-1 to 2-4 were performed and the results of which are reported in Tables F, G, H and J, respectively.

The abbreviations mentioned in the tables have the following meanings:

Ric: Rice 10 Mai: Tender Wh. Wheat

So. : Soybeans Cot .: Cotton Ra .: Radish 15 B.G .: panicum crus-galli linnaeus

Cr.G .: digitaria sanguinalis scopoli D.F .: alopecurus aequalis sobolewski var amurensis ohwi J.G .: sorghum halepense G.F .: chenopodium album linnaeus var centrorubrum makino.

20 TABLE F (Test 2 ~ 1) Action-Joseve VrinS. Ric. Mai. Wh. So. Cot. Ra. B.G. Cr.G. D.P. J.G. G.P.

dust | (Kg / ha) '..... “0.25 3' T ~ ö δ 0 0 ~ TÖ 10 10 Tö ö 25 1 0.125 0 oio 0 0 0 10 10 10 6 0 2 0.25 3 2 0 0 0 0 L0 10 10 10 0 __ 0.125 0__0 0 0 0 0_ 10 10 10 8 0 3 0.25 3 2 0 0 0 0 10 10 10 10 0 __ 0.125 0__0 0 0 0 0_ 10 10 10 7 0 4 0.25 2 2 0 0 0 0 10 10 10 10 0 30__0.125 0 0 0 0 0 0 IQ IQ IQ IQ p 0.25 2 2 0 0 0 0 10 10 10 10 0 5 0.125 0__0 0 0 0 0_ 10 10 10 10 0 6 0.25 1 2 0 0 0 0 10 10 10 10 0 __0.125 0 0 0 0 __0 0 10 10 10 10 0 „0.25 2 2 0 0 0 0 10 10 10 10 0 _ 0.125 0_ 0 0 0 0 0 10 10 10 9 0 35 '0.25 1 2 0 0 0 0 10 10 10 “10 0 8 0. 125 0__0 0__0_____0 0 10 10 10 7 0 0.25 2 2 0 0 00 10 10 10" 10 0 9 0. 125 0_0 0 0 0 0 10 10 10 6 0 V , 0.25 "5 ΓΊ -. 0 0 0 10 10 1Ö" 10 o

0.1251 0 01 0101 0 1 o 10 | 10 1 10 19 Q

7904242 r Ψ “29-20676 / Vk / ts

Continued TABLE F (Test 2-1) * Comparative compound indicated on the formula sheet with formula: | 'j II Μ lil [lil I0.25 2 3 2 0 Op-- 4 5 5 2 0 0.125 1 2 1 0 _0 0 2 3 3 1 0 • 5 0.25 4 3 3 0 0 0 5 6 6 ~ 3 0 10 0.125 2 1 2 0 _0 0 3 3 4 0 0 n 0.25 3 2 2 0 00 5 6 6 * 3 0 _ 0.125 1 010 _0 0 2 _2 3 1 0 18 0.25 4 3 3 0 0 0 5. 5 flT '4 0 __ 0.125 1 1 2 0 _0 0 3 2 2 2 0 - "TT 0.25 6 5 4 0 0 0 7 7 T 6 Ö- 10 10,125 2 1 2 I 3 1 0 1 0 1 0 1 2 1 3 1 4 14 10

J

TABLE G (Test 2-2) ^ Hummer Dosage | of the active compound Ric. Mai. Wh. So. Cot. Ra. B.G. Cr.G. D.F. J.Gi G.F.

thing (Kg / ha) 0.25 2 1 1 0 0 “0 ÏÓ TÖ 1Ö 10 Ö 14 0.125 1 0 0 0 0 10 10 10 10 9 0 2 0.0625 0 0 0 0_ 0 0 6 7 7 6 0 0.25 2 1 1 0 0 0 10 10 10 10 Ös 0.125 0 0 0 0 0 0 9 9 9 8 0 0.0625 00 00 00 4 5 6 4 0 0.25 2 1 1 0 0 0 10 10 ÏÖ 10 Ή) 16 0.125 10 00 00 9 9 10 8 0 0.0625 0 0 0 0 0 0 6 7 7 6 0 25 - ----------- --- TABLE H (Test 2-3)

Number Dosage * 11 't of the Active' compound Ric. Mai. Wh. So. Cot. Ra. B.G. Cr.G. D.F. J.G. G.F. * 30 pcs gg / ha ____ ° * 25 2 1 0 0 0 0 10 ïo ïo "iÖ" TÖ 17 0.125 0 0 0 0 0 0 10 10 10 10 '0 --- 1 0625 I 0 1 0 I 0 I 0 IQ o 1010 10 10 0 7904242 τ,? 'ρ * »-30- 20676 / Vk / ts TABLE j (Test 2-4)

Number Dosage 'of the -' Active compound Ric. Mai. Wh. So. Cot. Ra. B.G. Cr.G. D.F. J.G. G.F.

13In £ (Kg / ha) _: ___________________ 0.25 4 0 0 0.0 0 10 10 10 10 .0 5 18 0.125 0 0 0 0 0 0 10 10 10 10 '0 ~ 0.25 4 0 0 0 0 0 10 10 10 10 0 iy Λ tπk_O ^ La ^ 0 0 0 0 10 _ 10 10_, 10 o _ »2 3 1" "o * 0 0 2 ^ 4 3 J 2 ~ ---— '0 I 10 1 0 1 0 I 0 1 0 1 0 1 2 lil 01 10 * Comparative compound indicated on the formula sheet with formula.

EXPERIMENT III.

The tests in this experiment were performed against the plants and weeds to be harvested that appear on land at a stage • J5 after germination by performing a leaf treatment.

Each 600 cm pot was filled with soil and seeds of grain, barley, soybeans, radish, panicum crus-galli linnaeus and digitaria sanguinalis scopoli were introduced therein.

The emulsifiable concentrate prepared according to the method stated for composition II was diluted with water to obtain the specific concentration of the compound and the diluted solution was sprayed evenly at 1 kl / ha when the grassy weeds had grown to a 3-leaf stage and the dicotyledonous weeds had grown to the first divergence stage.

Fifteen days after the treatment, the herbicidal influence and the phytotoxicity of the plants to be harvested was determined and the valuation thereof was determined as stated in experiment 1.

The results of tests 3-1 to 3-5 are listed in Tables K, L, Μ, N and P, respectively, while the abbreviations listed in the tables have the following meanings:

Wh: Wheat Ba .: Barley

So .: Soybeans 35 Ra .: Radish B.G .: panicum crus-galli linnaeus Cr.G .: digitaria sanguinalis scopoli 790 4 2 42 '.-1 (~ 31 “20676 / vk / ts TABLE K (test 3-1).

Number of Concentration connection Wh .. Ba. So. Ra. B.G. Cr.G.

thing_ (ppm) _________ 5 500 0 0 0 0 10 10 _] __ 250 __0__0 0 0 10 10 2. 500 0 0 0 0 10 10 250 ____0__0 0 0 10 10 500 0 0 0 0 10 10 - 3 250 0 0 0 0 10. 10 '"J 50 0 0 0 0 0 10 10 - 250 0 0 0.0 10 10"; 500 0 0 0 0 10 10 5 250 0 0 0 0 10 10 6 500 0 0 0 0 10 10 _ 250__0__0 0 0 10 10 „500 0 0 0 0 10 10.

15 250 0 0 0 0 10 IQ

500 0 0 0 0 10 10 8 250 0 0 0 0 10 10 9 500 0 0..0 0 10 “JO:” * _ 250__0__0 0 0 10 10: n 500 0 0 0 0 10 ίο I 250 0 000 10 10 20 ...... * '"" "1 ί · - ——" --11 * *

Comparative compound indicated on the formula sheet with formula T 500 2 3 0 Ö 6 7 250__1__1__0 0__2___4___ l6 # 500 3 4 0 0 6 6 2ς _, 250__2__10 0__3__2 * 500 2 3 0 0 4 4 17, 250__0__10 0__1 2 18 * 500 3 4 0 0 5 6 ____250__2__2 0 0 6__4: * 500 4 4 0 0 6 6 19 __250 I 3 3 0 0 3 I 4) 30 s __ TABLE L (Test 3-2> _

Number from „, 1 y - -

the connection centers- I

thing ®, ^ apm; Wh. Sq> B.G. Cr.G.

^ 500 ÏÖ TÓ Ö Ö ”ÏÖ 'Ï0 35 _____250 ___10 10 0 0 10 10' 15 500 10 10 0 0 10 10 __2J50__10 10 0__0 10. _ 10 6 500 10 10 0 0 10" 10 __1 250 1 10 1 10 1 0 1 0 _10 10

'7 Q n L O h O

-32— 20676 / Vk / ts • t * TABLE M (Test 3-3)

Number of Concentration compound Wh., Ba. So, Ra. B.G, Cr.G.

thing (ppm) 5 ”Z 500 3 - 2 0 0 10 10 17 250 [0 1 o 1 0 1 0 I IQ 1 10 TABLE N (Test 3-¾).

IQ Number of Concentration Link (ppm) Wh <Ba. So. Ra> B.G. Cr.G.

thing 18 500 ~ 2 0 0 10 10 250__Q 1 0__0 10 10 19 500 10 9 0 0 10 r 10 ._ 250 6 8__0__0 10 10 g

For comparison, compound indicated on the formula sheet with formula: __ ~~~

* 500 T 4 4 6 7 10 10 I.

^ __ 250__2 I 2 1 3 1 3 10 10 1 20 TABLE P (Test 3-5).

Number of Concentra- the connection (dpm) wh fia. So. Ra. B.G. Cr.G.

thing 25 500 -0 - Ö 0 0 10 .10 22 250__Q 0__0 0 10 10 EXPERIMENT IV.

This experiment was carried out with plants to be harvested and 2Q weeds on land after germination by leaf treatment.

2

A pot made of polyethylene with a surface of 2000 cm was filled with soil and seeds of rice, tender, wheat, soybeans, cotton, radish, panicum crus-galli linnaeus, digitaria sanguinalis scopoli, alopecurus aequalis sobolewski var amurensis ohwi, were placed therein. sorghum halepense, chenopodium album linnaeus var centrorubrum makino, using 25 790 42 42 - 5- ς: / -33- 20676 / Vk / ts seeds from each plant.

An emulsifiable concentrate was prepared following the procedure indicated for composition number 2 and diluted with water to obtain a concentration of 125-62r5 'and 31-25 ppm and the dilute solution was sprayed evenly in an amount of 20. 0 ml per pot when the plants had grown to such a stage that they had 2-4 leaves.

Twenty days after treatment, the herbicidal influence and the phytotoxicity of the plants to be harvested was determined and the rating for this is given in the tables and determined as indicated in experiment I.

10 Tests 4-1 to 4-5 are listed in Tables Q, R, S, T, and 0, respectively, and the abbreviations listed in these tables have the following meanings: ƒ

Ric .: Rice

Mai: Corn 15 Wh .: Wheat

So .: Soybeans Cot .: Cotton Ra .: Radish B.G. panieum crus-galli linnaeus 20 Cr.G .: digitaria sanguinalis scopoli D.F .: alopecurus aequalis sobolewski var amurensis ohwi J.G .: sorghum halepense G.F .: chenopodium album linnaeus var centrorubrum makino.

TABLE Q (Test 4-1).

25 Number of Concentra- ~ · ·, _ I _ I _ the connection W * 1 · So * Cot · Ra * B * G · Cr * G · D.F. J.G. G.F.

thing "Ï25! δ ö δ" ö io Tö Tö! ó ö __62.5 0 0 0 0 10 10 10 10 1 9 0 2 125 0 0 0 0 10 Ï0 TÖ 10 0: 30__62.5 0 0 0 0 I 10 1 10 10 9 0 3 125 Ö 0 1 0 10 10 10 9 0 ___ 62.5 0 0 0 0 10 10 10 8 0 4 125 0 0 0 0 10 10 10 10 0 62.5 0 0 0 0 10 10 10 IQ p 5 125 0 0 Ö “0 10 10 10 10 Ö · 62.5 _0 0 0 0 10 10 IQ io p 35 6 125 0 0 0 0 10 10 10 10 Ó __62.5 0 0 0 0 10 _U) 10 10 0 7 125 0 0 (ΓΊ 0 10 10 10 10

_I 62.5 I 0 I 0 I 0 Q IQ 10 1 10 1 9 Q

7904242 I. r 'V - - ...': ... . .

-34- 20676 / Vk / ts

Continued TABLE Q (Test 4-1) number of Iconcentra-j ,,. "_, _" Γ I f f the connection (dpm) Λ · So * Cot 'Ra * G-B' Dr.G. j D.F .. J.O. I G.F.

thing_: 125 0 0 0 0 10 10 10 ~ ίθ 0 ®__62.5 _0 0 _0 1 0 10 10 10 10 0 1 “125 0 .0 0 0 10 10 10 10 0 __62.5 _0 0 _0 0 10 10 10 8 0 H 125 0 0 0 0 10 10 10 10 0 _1 62.5 1 0 I 0 I 0 1 0 1 10 10 10 .7 0 * Comparative compound indicated on the formula sheet with formula »ΓΤ25 2 I 0 I <ΓΊ (Π ΓΊ 4 | -4. '| 4 0 1n 15 62.5 1 0 0 0 1 2 2 1 0 16 * 125 3 0 (ΓΊ Γ 5 6 6 5 0 62.5 _2 0 _0__0 3 4.3 2 0 17 * 125 2 0 0 0 4 5 6 * 4 0 _ 62.5 0 0 _0___0 2 2 3 2 0 s # 125 2 0 0 0 5 5 5 4 0 ____ 62.5 1 O _0___0 3 2 3 1 0 15 19 * 125 3 0 0 0 6 7 7 6 0 '' _] 62.5 I 2 I 0 0 0 4 14 3 4 0 | TABLE R (test 4-2)

Number of uncentrated connection, ie Ric. Mai. Wh. So. Cot. Ra. B.G. Cr.G. D.F. J.G. G.F.

20 thing (ppm) "'125 Το ΪΊΓ- 7 ö ö o ΠΓ 10 10 Tö' ö" 11 »62.5 7 6 3 0 0 0 10 10 10 10 0. 31.25 4 3 _0 0 0_ 0 10 10 10 10 0 15 "T25 110 10 6 ~ 0 0 0 10 1010 10 o 62.5 6 5 3 0 0 0 10 10 10 10 0 25 _j 31.25 3 2 _0 0 0_ 0 10 10 10 10 _0__ 6 125 10 10 6 0 0 0 10 10 10 10 0 1 62.5 6 5 3 0 0 0 10 10 10 10 0 _ 31.25 3 2 0 0 0 0 10 10 10 10 0 TABLE S (test 4-3) 3 °

Number Concentra "" "" "" of the tie idpm) Λί ° · Mai. Wh. So. Cot. Ra. B.G. Cr.G. D.F. J.G.

connect -___; __; _____ thing 125 1 0 0 0 0 0 10 10 10 '"TÖ 17 62.5 0 0 0 0 0 0 10 10 10 10 35 _ 31.25 0_0 0 0 0 0 _10__10__10 10 790 4 2 42 -t - > rr, -35- 20676 / Vk / ts TABLE T (Test 4-4)

Number Concen— of Ric. Mai. Wh. So. Cot. Ra. B.G. Cr.G. D.F. J.G. G. ^. connection: (ppm) __ · ____- _ ___ thing - 4 5 0 0 0 10 10 10 10 0 5 18 62.5 0 00 00 010 10 AjL · __IQ__2— ---- 125 ΓΊ Γ "0 0 0 0 10 10 10 10 0 62.5 0_0__0__0__0__0 10 10 10 IP__2_ --20--125 3 15 0__0__0__0 10 10_ 10 10__2_ --51— '125 4 6 0 0 0 I 0 1 10 1- 10 · 10 -1 10____ 5 "" 125 3 2 4 0 0 0 4 4 '5 3 0 20 62.5 1 0 2 -0-1- 0 · 0 -I · - -2' 1 · 3 1 · 4 I 1 I 0 ____.

* * Comparison given on the formula sheet with formula TABLE ü (Test 4-5).

* "Flummêr- uoncentiS- ι I I

van der tie · (ppm) Mai. wh_ ^ Cot. Ha_ B, G. Cr.G. D.F, J.G. G.F.

connection - 125 "" '- 1 - ö 5 "δ δ δ Ιό Tö Tif ~ lö ~ ί 22 62.5 0 0 0 0 0 0 10 10 1U 10 0 31.25 0 0 0.0 0 0 10 1 ° 10, 10 0 - CONCLUSIONS - \ 4 790 42 42

Claims (13)

1. Process for preparing a pyridyloxyphenoxy unsaturated derivative, characterized in that the derivative of formula 1, indicated on the formula sheet, wherein Z is CH 2 OH, COOR or -COSR 'and R is a hydrogen atom an organic or inorganic salt an alkyl, haloalkyl, alkenyl, alkynylphenyl, halo-phenyl, alkylphenyl, benzyl, alkoxyalkyleneoxyalkyl, pyridylmethyl or alkoxyalkyl group and R 'is an alkyl group is prepared by an unsaturated halide of the formula II wherein Z 'has the same meaning as Z or is a group convertible to Z and Hal represents a halogen, to react with a pyridyloxy-2-phenol of formula 3> in the presence of a hydrogen halide. agent such as a base at a temperature of 100-150 ° C and optionally Z 'is converted to Z by an esterification, a hydrogenation, a neutralization or an amidation. 2. Process according to claim 1, characterized in that a pyridyloxyphenoxy-unsaturated acid of the formula 4 or the acid halide thereof of the formula 9 is prepared by reacting it. unsaturated halide of formula Hal-CHCH · CHC00H 20 and the pyridyloxy-2-phenol of formula 3> indicated on the formula sheet, and if necessary a halogenating agent, reacts with the resulting pyridyloxyphenoxy unsaturated acid of formula 4 and then the compound of formula 4 or convert formula 9 to the desired compound. 3. Process according to claim 2, characterized in that the compound of formula 4 or 9> indicated on the formula sheet, is reacted with a compound of formula ROH or RVSH, wherein R and R 'have the same meaning as indicated above , whether or not in the presence of an inert solvent, at a temperature of 0-150 ° C. 30 4. Process according to claim 2, characterized in that the compound of formula 4 or 9 is hydrogenated to obtain a pyridyloxyphenoxy unsaturated alcohol of formula 8, indicated on the formula sheet and if necessary reacted the unsaturated alcohol of formula 8 with 35 R '"H or H" Hall. 790 4 2 42 -37- 20676 / Vk / ts ry 'C *' K i r Pyridyloxyphenoxy unsaturated derivative, characterized in that it corresponds to formula 1, indicated on the formula sheet, where Z has the meaning of -CHgOH, COOR or -CQSRf and R represents a hydrogen atom or a salt derived from an organic or inorganic acid, an alkyl, haloalkyl, alkenyl, alkynyl, phenyl-r, halophenyl, alkylphenyl, benzyl, alkoxyalkyleneoxyalkyl, pyridylmethyl or alkoxyalkyl group and Rr represents an alkyl group. Pyridyloxyphenoxy unsaturated derivative according to claim 5, characterized in that it is a pyridyloxyphenoxy unsaturated derivative of formula 11, 10 indicated on the formula sheet, wherein R has the same meaning as indicated above. J Pyridyloxyphenoxy unsaturated derivative according to claim 5, characterized in that it is a pyridyloxyphenoxy unsaturated derivative of formula 12, 15 indicated on the formula sheet, wherein Rr has the same meaning as indicated above. Pyridyloxyphenoxy unsaturated derivative according to claim 5, characterized in that it is a pyridyloxyphenoxy unsaturated derivative of formula 13,20 indicated on the formula sheet. 9. A method of preparing a herbicidal composition, based on an active herbicide and the desired auxiliary substances, characterized in that as active herbicide a compound of formula 1 is used, indicated on the formula sheet, wherein the meaning of Z, R and R 'are the same as indicated for claim 1. 10. Herbicidal composition according to claim 9, characterized in that the active component used is a pyridyloxyphenoxy unsaturated derivative of formula 11, indicated on the formula sheet. Herbicidal composition according to claim 9, characterized in that the active compound used is a pyridyloxyphenoxy unsaturated derivative of formula 13, indicated on the formula sheet. 35 7904242 - V * «: - -38- 20676 / Vk / ts A method of controlling weeds by carrying out a soil treatment or a foliar treatment with a herbicidal composition, characterized in that a herbieidal active component is used and the active substance is applied in an amount of 0.01 up to 10 kg / ha. 5 A method according to claim 12, characterized in that the herbicidal effective amount of the active substance is 10-10000 ppm in a foliar treatment. ·. * 7904242