CS210604B2 - Herbicide and preparation method of active substance - Google Patents

Description

The invention relates to a novel herbicidal composition.

In particular, it relates to novel 4- (5-fluoromethyl-2-pyridyloxy) phenoxyalkanecarboxylic acids and their derivatives which are useful as herbicidal active substances in agriculture and horticulture, as well as herbicidal compositions which the said acids and their derivatives contain; The invention also relates to a method for controlling weeds using said herbicidal compositions.

In recent years, a considerable number of new herbicidal compositions have been developed and put into practice. As a result of the application of these herbicidal compositions, labor savings and increased agricultural production have been achieved. However, there is a continuing demand for · other new herbicidal compositions that would have a reduced deleterious effect on crop plants while maintaining or increasing the herbicidal effect on undesirable plants and · that would not contaminate agricultural land with harmful chemicals.

For example, phenoxyalkanecarboxylic acids, exemplified by 2,4-dichlorophenoxycarbonylic acid, and which have been known for some time, have an excellent herbicidal effect on broadleaf weeds and have a wide range of applications. However, these phenoxyalkanecarboxylic acids show only a low degree of herbicidal activity against the grass weeds which are mainly considered to be harmful weeds; Said phenoxyalcancarboxylic acids are also phytotoxic to broad-leaved crop plants including many kinds of cereals and cultivated trees. Due to the limited versatility of these herbicidally active acids, the herbicidally active compounds can only be used with certain limitations.

Therefore, they have been proposed in recent years as 4-phenoixyylcancarboxylic acid herbicides which are also herbicidally active against grass weeds and are not phytotoxic to broad-leaved crops; such herbicidally active compounds are described, for example, in U.S. Pat. No. 3,954,442.

A further improvement of the properties of this type of herbicidally active compounds is described in U.S. Pat. No. 4,046,553, but even the compounds described herein do not have entirely satisfactory properties.

The subject of the invention is a herbicidal composition comprising a herbicidally effective amount of at least one compound of the formula I,

R О o ΗίαΗρζ ¹ (I) in which means

X is fluorine or chlorine,

Y is hydrogen or chlorine, n is 0 or 2,

R is hydrogen, methyl or ethyl,

Z ^{1 is a} hydroxyl group, an alkoxy group having from ^{1 to 5} carbon atoms; 6 carbon atoms, the alkyl radical of which may be substituted by 1 to 3 halogen atoms, alkoxyalkoxy, each alkoxy group having 1 to 4 carbon atoms, alkenyloxy of 4 to 4 carbon atoms, alkynyloxy of 2 to 4 carbon atoms, cycloalkoxy; C 3 -C 6 cycloalkyl radical of which the cycloalkyl radical may be substituted by an alkyl. C 1 -C 4, alkoxycarbonylalkoxy, wherein each alkoxy group has

1- to 4 carbon atoms, a phenoxy group whose aryl radical may be substituted by 1- to halogen atoms or a C1-C4 alkyl group, benzyloxy, glycidylcixy, C1-C4 alkylthio group, C2-C4 alkenylthio group , a phenylthio group whose aryl radical may be substituted by 1 to 3 halogen atoms or a (C1-C4) alkyl group, an amino group, a (C1-C4) alkylamino group, an alkoxycarbonylmethylamino group wherein the alkyl group has 1 to 4 carbon atoms, a hydroxycarbonylmethylamino group an anilino group, the aryl radical of which may be substituted by 1 to 3 halogen atoms, a pyridin-2-ylamine group, an -O-catlon or a halogen atom, and an agriculturally acceptable additive.

Preferably, the herbicidal composition comprises a herbicidally effective amount of at least one compound of formula I in which it is

X is fluorine,

Y is hydrogen or chlorine,

R is methyl, n O,

Z1 is a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, the alkyl radical of which may be substituted by 1 to halogen atoms, an alkoxyalkoxy group wherein each alkoxy group has 1 to carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, an alkynyloxy group having 2 to 4 C 4 -C 6 -cycloalkoxy of which the cycloalkyl radical may be substituted by C 1 -C 4 alkyl, phenoxy, the aryl radical of which may be substituted by 1 to 3 halogen atoms or C 1 -C 3 alkyl C 4 -C 4 alkyl, benzyloxy, glycidyloxy or -O-cation.

The herbicidal composition according to the invention particularly preferably comprises a herbicidally effective amount of at least one compound of formula I in which

X is fluorine,

Y is hydrogen or chlorine,

R is methyl, n O,

Z ¹ · a hydroxyl group, an alkoxy group with 1-4 carbon atoms, alkenyloxy having 2 to 4 carbon atoms, cycloalkoxy having 3 to 6 carbon atoms or an -O-cation.

The herbicidal composition of the invention preferably comprises a herbicidally effective amount of - o - [4- (5-trifluoromethyl-2-pyridyloxy) phenoxy] -propionic acid, - and - [N - (3-chloro-5-trifluoromethyl-2)] sodium [4- (5-trifluoromethyl-2-pyridyloxy) phenoxy] propionate, - [alpha] - [4- (3-chloro-5-trifluoromethyl-2-pyridyloxy) phenoxy] propionate - methyl-α- [4- (5-trifluoromethyl-2-pyrldyloxyphenoxy) propionate, - methyl- [4- (3-chloro-5-trifluoromethyl-4-pyridyloxy) phenoxy] propionate, - ethyl N - [4- (5-trifluoromethyl-2-pyridyloxy) phenoxy] propionate, as well as - ethyl-.beta.-N-chloro-S-

(trifluoromethyl-2-pyridinyl) phenoxy] propionate.

The invention also relates to a process for the preparation of the above-mentioned active compound of the formula I

R О

I I11

OCHÍCHJ ^ CZ

(I) in which is

X is fluorine or <chlorine,

Y is hydrogen or chlorine,

Z is hydrogen, methyl or ethyl, n 0 or 2,

Z ¹ hydroxyl group, alkoxy group having 1 to 6 carbon atoms, whose alkyl moiety may be substituted with 1 to 3 halogen atoms, alkoxyalkoxy groups where each _alkoxy: having from 1 to 4 carbon atoms, alkenyloxy having 2 to 4 carbon atoms, (C 2 -C 4) alkynyloxy, (C 3 -C 6) cycloalkoxy, the cycloalkyl radical of which may be substituted by C 1 -C 4 alkyl, alkoxycarbonylalkoxy, each C 1 -C 4 alkoxy, phenoxy, aryl the radical may be substituted with 1 to 3 halogen atoms or a (C1 -C4) alkyl group, benzyloxy, glycidyloxy, (C1 -C4) alkylthio, (C2 -C4) alkenylthio, phenylthio, the aryl radical of which may be substituted with 1 to 4 carbon atoms Or (C1 -C4) -alkyl; carbon atom, amino group, C 1 -C 4 alkylamino group, alkoxycarbonylmethylamino group wherein the alkoxy group has 1 to 4 carbon atoms, hydroxycarbonylmethylamino group, aniline group whose aryl radical may be substituted by 1 to 3 halogen atoms, pyridine-2- ylamino, -O-cation or a halogen atom, characterized in that the 2-halo-5-fluoromethylpyridine of the formula II is first condensed,

(III) wherein

Q represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or a group

RO — OCH (CH2) _n CZ ⁴ , in which

Wounds have the meaning given above and

Z ⁴ represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an amino group, in the presence of an alkali to form a substituted pyridylphenyl ether of formula IV,

in which

X, Y and Q are as defined above, where Q is other than a group

R O

I II — OCH (CH2) _n CZ ^,

condenses a substituted pyridyl phenyl ether of formula IV and a haloalkanecarboxylic acid or a derivative thereof of formula VII, (II) in which:

Hal means a halogen atom,

X and Y are as defined above, and substituted phenol of formula III,

R O

I II

Hal - CH (CH 2) _n CZ ⁴ (VII) wherein

Hal, R, and Z ⁴ are as defined above,

210804 or γ-valerolactone in the presence of an alkali to form a compound of formula V wherein

Hal, X and Y are as defined above,

R O

I> ¹¹ 4

OCH (CH) CZ ^ (V) in which

X, Y, R, to Z ⁴ are as defined above, or salts thereof, optionally converting the Z ⁴ residue of a compound of formula V to the Z ¹ residue, wherein Z ¹ is as defined above, by a conventional method for neutralizing, halogenating, an amination, thioesterification, eisterlification or reesterification reaction.

In the process according to the invention, the 2-halo-5-fluoromethylpyridine of the formula II is preferably condensed with p-hydroxyphenoxyalkanecarboxylic acid or a derivative of the formula X,

in which

N to Z ⁴ are as hereinbefore defined, in the presence of an alkaline substance at a temperature of a- «At least a 50 ^Q C for 1-20 hours to give compound of formula V,

(II)

in which

X, Y, R to Z ⁴ are as defined above; and thereafter optionally converting the radical Z ⁴ Formula V compound to the radical Z ⁴ wherein Z ¹ is as defined above, known method for · neutralizing amination, thioesterification, an esterification or re-esterification reaction.

The process according to the invention can also advantageously be carried out by condensing 2-halo-5-fluoromethylpyridine of the general formula II and hydroquinone in the presence of an alkali at a temperature of at least 50 ° C for 1 to 20 hours to form a substituted pyrldyl-p- hydroxyphenyl ether of general formula

(VI)

in which

X and Y are as defined above, whereupon the compound of formula (VI) is condensed with a haloalkanecarboxylic acid or a derivative of formula (VII), wherein:

Hal, X and Y are as defined above,

210604 9 10  ............. R O 1 II or with β-valerolactone in the presence of an alkali at a temperature of 40 to 200 ° C for a period of time Hal - CH (CH 2) _n CZ ⁴ (VII) 0.5 to 10 hours to give a compound of formula V,

in which

Hal, R, and Z ⁴ are as defined above,

in which

X, Y, R, to Z ⁴ are as defined above, whereupon optionally the Z ⁴ moiety of the compound of formula V is converted to the Z ¹ moiety as defined above by a known method for neutralization, halogenation, amination, thioesterification, esterification and a re-esterification reaction.

The process according to the invention can also be carried out by condensing 2-halo-5-fluoromethylpyridine of the formula P,

Hal, X and Y are as defined above with the hydroquinone monoalkyl ether of formula XI,

(XI) wherein alkyl is an alkyl group having 1 to carbon atoms, in the presence of an alkali at a temperature of at least 50 ° C for 1 to 20 hours to form a substituted pyridyl-p-alkoxy-phenyl ether of formula XII,

(XII) alkyl has the same meaning as X and Y, whereupon the compound of formula (XII) is dealkylated to give a substituted pyridyl-p-hydroxyphenyl ether of formula (VI),

Y

(VI) in which:

X and Y are as defined above, and the compound of formula VI is then condensed with a haloalkanecarboxylic acid or a derivative of formula VII,

R o

I II

Hal — CH (CH ₂ ) _n CZ ⁴ (VII) wherein

Hal, R to Z ⁴ are as defined above, or with a χ-valerolactone in the presence of an alkaline substance at a temperature of 40-200 ° C for 0.5 to 10 hours to form a compound of formula V,

in which

X, Y, R, to Z ⁴ are as defined above, whereupon optionally the Z ⁴ moiety of the compound of formula V is optionally converted to a Z ¹ moiety as hereinbefore defined by a method known per se for neutralizing, balding, amination , a thioesterification, esterification or reesterification reaction.

In the process according to the invention, the alkali metal hydroxide or alkali metal carbonate is preferably used as the alkali in the first and second condensations.

The compound of formula (I) which is useful as a herbicidally active compound according to the invention is a novel compound and exhibits a unique herbicidal activity which differs from the herbicidal activity of hitherto known types of herbicidal compounds. The herbicidally active compound of the invention has the following three important characteristics.

1) The compound of formula (I) has a strong selective herbicidal activity against grass weeds. Therefore, since it has very little effect on broad-leaved crops, it can be used with a guarantee wherever weeds need to be controlled in the presence of broad-leaved crops, including broad-leaved cereals and cultivated trees. In other words, the compound of formula I has a completely opposite selectivity to the aforementioned known phenoxyalkanecarboxylic acids; however, this selectivity is much higher than that of the acids.

2) The compound of formula (I) has a high translocability in the plant structure. This compound is absorbed by the foliage and roots of the plant, mainly causing the death and decomposition of the meristatic cells in the plant nymphs, resulting in drying, wilting and finally death of the plant. Therefore, it is sufficient if the compound of formula I is applied only to a very limited part of the plant; in this case too, the compound of the formula I has a strong herbicidal activity which, after application, results in wilting and undesired weeds.

(3) The compound of formula (I) has excellent prolonged herbicidal activity against perennial weed weeds, showing substantially no phytotoxicity to cotton as compared to known 4-phenoxy- or 4- (2-pyridyloxy) phenoxyalkanecarboxylic acids. which is generally very difficult to kill, the compound of formula I has a higher translocability than 4-phenoxy- or 4- (2-pyridyloxy) phenoxyalkanecarboxylic acid, and in each part of the plant to which it is translocated acts to such an extent that the plant, including its roots, withers and dies, thus providing a prolonged effect to prevent the plant from growing over the next season, therefore, the compound of the formula is particularly suitable for eradicating unwanted plants with the least possible number of herbicide applications.

In the above definition of the substituents of formula (I), suitable examples of halogen atoms which may be used as substituents for the alkoxy group of 1 to 6 carbon atoms, phenoxy, phenylthio or the aniline group mentioned for the substituent Z ¹ , chlorine, a fluorine atom, a bromine atom and an iodine atom, with chlorine being a preferred example of a halogen atom.

Suitable examples of alkyl groups which may also be used as substituents for the C 3 -C 6 cycloalkyl, phenoxy or phenylthio group mentioned for the general substituent Z ¹ are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, with methyl and ethyl being preferred examples of alkyl.

Suitable examples of cations for the -O-cation group are an alkali metal ion such as sodium and potassium ion, an alkaline earth metal ion such as calcium or magnesium ion, ammonium and an organic ion such as dimethylammonium or dlethanolammonium ion.

The herbicidal compound of formula (I) may be commercially used as an active ingredient of the herbicidal compositions as will be apparent from the tests below.

Among the compounds of formula (I), preferred compounds are those of formula (Ia),

¹¹ Sep

OCHCZ * in which means

Y is hydrogen or chlorine; and

Z is ² hydroxyl, alkoxy of 1 to 4 carbon atoms, alkenyloxy of 2 to 4 carbon atoms, cycloalkoxy of 3 to 6 carbon atoms, or -O-cation.

Particularly preferred compounds of formula I are those of the following formula Ib,

in which it means

Y is hydrogen or chlorine; and

Z ³ hydroxyl group, alkoxyl group, or an -O-cation.

Typical examples of compounds of formula (I) according to the invention are those listed in the following table:

Merge-X to number o

Physical constants

1 -F - H —H 0 —OH mp 123-124 ° C 2 -F - H —CH3 0 —OH mp 97-100 ° C 3 -F —Cl —CH3 0 —OH mp 107-109 ° C 4 -F —H —C2H5 0 —OH mp 95-97 ° C 5 -F —H —CH3 2 —OH mp 231-235 ° C 6 -F —Cl - CH5 2 —OH 7 - Cl —Cl —CH3 0 —OH mp 103-106 ° C 8 -F —Cl —H 2 —OCH3 b. 189-192 ° C / / 133 Pa 9 -F —H - CH3 0 —OCH3 mp 72-74 ° C b. 175-177 ° C / / 267 Pa 10 -F —Cl —CH3 0 —OCHs mp 67-69 ° C 11 -F —H —H 0 —OC2H5 mp 55-58 ° C 12 -F —H —CH3 0 —OC2H5 mp 63-65 ° C b. 182-185 ° C / / 400 Pa 13 -F —Cl —CH3 0 —OC2H5 b. 168-170 ° C / / 133 Pa 14 -F —H —C2H5 0 —OC2H5 n _D 20 1.5042 15 Dec -F —H. —CHs 2 —OC2H5 b. 150-153 ° C / / 133 Pa 16 -F —Cl —CH3 2 —OC2H5 b. 161-164 ° C // 133 Pa 17 —Cl —Cl —CH3 0 —OC2H5 b. v. 174—176 ° C / / 133 Pa 18 -F —Cl —CH3 0 - 0 — C3H7 (n) b. 205-207 ° C / / 267 Pa 19 Dec -F —Cl —CH3 0 —0 — C3H7 [iSO] b. v. 164-167 ° C / / 133 Pa 20 May —Cl —Cl —CH3 0 • —ϋ — ΗίΗ ^ η) b. 184-187 ° C / / 133 Pa 21 -F —H —CH3 0 —0 — C41 ^! ^ (N) b. 160-163 ° C / / 133 Pa 22nd -F —Cl —CH3 2 —0 — C4H9 (n) b. 194-197 ° C / / 133 Pa 23 -F —H —CH3 0 —OCH2CC13 b. 205-208 ° C / / 400 'Pa 24 -F - Cl —CH3 0 —OCH2CF3 b. 159-162 ° C / / 133 Pa 25 -F —H —CH3 0 —OCH2CH2OC2H5 b. 185-187 ° C / / 267 Pa 26 -F —H —CH3 0 —OCH2CH = CH2 b. 198-120 ° C / / 400 Pa 27 Mar: -F —Cl —CH3 0 —OCH2CH = CH2 b. 158-162 ° C / / 133 Pa 28 -F - Cl —CH3 2 —OCH2H = CH2 b. 169-173 ° C / / 133 Pa 29 -F —H —CHs 0 —OCH2CsCH n _D 2 ° 1.5212 30 —Cl —Cl —CH3 0 —OCH2C-CH b. 169-172 ° C / / 133 Pa 31 -F —Cl - CH3 0 —OCH2C = CH b. 161-163 ° C /

/ 133 Pa

Physical constants —СНз —SCH2CH = CH2 — NHCH2COOH

b. 232-235 ° C / / 400 Pa

b. 201-204 ° C // 133 Pa

mp 205-209 ° C / / 267 Pa

b. 224-228 ° C // 133 Pa

m.p. 207-210 ° C / / 133 Pa

b. 180-184 ° C / / 2 Pa · NH 2 -NH-C4Hg (n) -NH-C 1 H 9 (n) —NHCH 2 COOC 2 H 5

mp 182-185 ° C // 133 Pa n _D ²⁰ 1.54 3 5

b. 174-177 ° C / / 133 Pa

mp 187-191 ° C // 133 Pa n _D 20 1.5220

Compound number X CF ₂ X-Y R 32 -F —H —СНз 33 -F —Cl —СНз 34 -F —H —СПз 35 -F - H —СНз 36 -F —Cl —СНз 37 -F —H —СНз 38 -F —H —СНз 39 -F —Cl —СНз 40 -F - H —СНз 41 -F —Cl —Н 42 -F —Cl —Н 43 -F —H —СНз 44 -F —Cl —СНз 45 -F - Cl —СНз 46 -F - H —СНз 47 -F —H —СНз 48 -F —H —СНз 49 - F —H —СНз 50 -F —H —СНз

mp 211-213 ° C / / 133 Pa

—OCH2CH — OH2 \ z o —SC2H5 —S — СзН7 (п1

Physical constants

Merge-X to a number

Y

51 -F —H —СНз 0 52 -F - Cl —СНз 0 53 -F —H —СНз 0 54 -F —H —СНз 0 55 -F —H —СНз 0 56 -F —H —СНз 0 57 -F —Cl —СНз 0 58 -F - H —СНз 2 59 -F - H —СНз 0 60 -F —H —СНз 0 61 -F —H —СНз 0 62 -F - H —СНз 0 63 -F —Cl -СНз 0

mp 95-97 ° C

mp 139-141 ° C

mp 133-135 ° C

Cl

—СГК + —0 ~ Na + —ONa + —0Na ⁺ —0 ~ NH4 ⁺ —O-NH2 (CH3) 2 ⁺ —Cl — OCH2COOC2H5

C2H5

I — OCHCOOC2 H5

b. 210-215 ° C / / 267 Pa

m.p. 45-50 ° C

m.p. 70-75 ° C

m.p. 100-105 ° C

b. 300 ° C or greater

mp 54-57 ° C

b. 181-184 ° C / / 267 Pa

The herbicidally active compounds of the formula I according to the invention,

in which

X, Y, R, and Z ¹ are as defined above, may be prepared from Methods A and B below, with Method A being the more preferred method.

Method A

2-halo-5-fluoromethylpyridine of formula (II) wherein:

Hal represents a halogen atom and

X and Y are as defined above, and substituted phenol of formula III,

in which

Q represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms or a group

RO I II -OCH (CH ₂₎ ⁴ ₁ GB in which

Wounds have the meaning given above and

Z ⁴ represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms or an amino group, (II)

210В04

are first condensed, for example using equimolar amounts of a compound of formula II and a compound of formula III, in the presence of an alkali in an amount equal to 1- to 1.2 molar times the amount of a compound of formula III to form a substituted pyridylphenyl ether

in which

Y, X and Q are as defined above.

In case Q represents a group in which

Hal, R to Z ⁴ are as defined above, or χ-valerolactone are condensed, for example using equimolar amounts of a compound of formula VI and formula VII or χ-valerolactone, in the presence of an alkaline substance in an amount equal

1- to 1.2-fold times the amount of the compound of formula (VI), with or without prior dealkylation (i.e., removal of the alkyl moiety of the C 1 -C 6 alkoxy group) to give the compound of formula (V) or a salt thereof.

Method В

Trifluoromethyl iodide is reacted with a compound of formula VIII,

R 11 - OCH (CH 2) _n C ⁴ gives a compound of formula V in which

r í?

I ¹¹ 4OCH (CH ^ CZ (VIII))

o. H L (CH, LCZ *)

X, Y, R to Z ⁴ are as defined above.

If desired, the resulting product of formula (V) may be treated by a method known per se to effect the conversion of Z ⁴ to Z ¹ to give a herbicidally active compound of formula (I).

When Q represents a C 1 -C 6 alkoxy group or a hydroxyl group, the resulting substituted pyridyl-p-hydroxyphenyl ether of formula VI, wherein:

T represents a bromine or iodine atom, and Y, R to Z ⁴ are as hereinbefore defined, in the presence of a copper powder and a polar aprotic solvent such as pyridine, sulfolane, dimethylformamide or dimethylsulfoxide at a temperature of 100 to 200 ° C for 1 up to 24 hours to form a compound of formula IX,

(IX)

(VI) in which:

Y, R to Z ⁴ are as defined above.

If desired, the general substituent Z ⁴ in the general formula IX can be converted to the general substituent Z ¹ in a manner known per se to obtain a herbicidally active compound of the general formula I.

In the following, the processes for the preparation of the compounds of formula (I) and of the intermediates required for this preparation will be described in more detail.

in which

X and Y are as defined above, and haloalkanecarboxylic acid or a derivative of the formula VII,

R O

I II

Hal — CH (CH 2) _n CZ ⁴ (VII)

Compound of Formula V

Method A-1 or a salt thereof can be prepared by condensation of a substituted pyridine of formula II,

R O OCH (CH ^ CZ ^

(V) (1f) wherein

X, Y, R, on Z ⁴ are as defined above, may be prepared by condensation of a substituted pyridine of formula II,

(II) in which

Hal, X and Y are as defined above, p-hydroxyphenoxyalkanecarboxylic acid or a derivative of the general formula

in which

R 1 and Z ⁴ are as defined above, wherein the compound of formula II is used in an equimolar amount relative to the compound of formula X / in the presence of an alkali in an amount equal to

1- to 1.2 molar fold. of the compound of formula X at a temperature of at least 50 ° C, preferably at a temperature of 70 to 180 ° C, at a pressure preferably atmospheric for 1 to 20 hours, preferably for 1 to 10 hours.

Method A-2

Compound of Formula V

R

OCH (CHj _n ČZ in which

Hal, X and Y are as defined above, with hydroquinone, wherein the compound of formula II is used in an equimolar amount to the hydroquinone, in the presence of an alkali in an amount equal to 1 to 1.2 times the amount of hydroquinone at at least 50 ° C, preferably at a temperature of 70 to 180 ° C, in an inert atmosphere, such as a nitrogen atmosphere, for 1 to 20 hours to form a substituted pyridyl-p-hydroxyphenyl ether of formula VI,

У

(VI) in which:

X and Y are as defined above, and then condensing a compound of formula (VI) with a halocarboxylic acid or a derivative of formula (VII),

R O

I. II

Hal-CH (CH 2 and CH 2 ⁴ (VII) in which

Hal, R 1 and Z 4 are as defined above, or with γ-valerol, wherein the compound of formula VI is used in an equimolar amount relative to the amount of the compound of formula VII -or relative to the amount of χ- valerolactone; said condensation is carried out in the presence of an alkaline substance in an amount equal to 1- to 1.2 times the amount of the compound of the formula VI at a temperature. 40 to 200 ° C, preferably at atmospheric pressure for 0.5 to 10 hours.

(V) in which

X, Y, R to Z ⁴ are as defined above,

Method A-3

Compound of Formula V

осн

in which

X, Y, R to Z ⁴ are as defined above, or a salt thereof can be prepared by condensing a substituted pyridine of formula II

(II) in which

Hal, X and Y are as defined above, with a hydroquinone monoalkyl ether of formula XI,

(XI) wherein "alkyl" is an alkyl group having 1 to carbon atoms, wherein the compound of Formula II is used in an amount equal to an equimolar amount relative to the amount of the compound of Formula XI; said condensation is carried out in the presence of an alkali in an amount equal to 1- to 1.2 mole times the amount of the compound of formula XI at a temperature of at least 50 ° C, preferably 70 to 180 ° C, preferably at atmospheric pressure for 1 to 20 hours, preferably 1 to 10 hours, to form a substituted pyridyl-p-alkoxyphenyl ether of formula XII,

in which

X, Y and "alkyl" are as defined above, by dealkylating a compound of formula XII to form a substituted pyridyl-p-hydroxyphenyl ether of formula VI, (V)

(VI) in which:

X and Y are as defined above, and then condensation of a compound of formula VI with a haloalkanecarboxylic acid or a derivative of formula VII,

R O

I II

Hal-CH (CH 2), CZ ⁴ (VII) wherein

Hal, R to Z ⁴ are as defined above, or with y-valerolactone, wherein the compound of formula VI is used in an equimolar amount к amount of a compound of formula VII or relative quantity к χ-valerolactone; said condensation is carried out in the presence of an alkaline material in an amount equal to 1- to 2

At a temperature of 40 to 200 ° C, preferably at atmospheric pressure for 0.5 to 10 hours.

Examples of suitable alkali materials which may be used in the above condensation reactions are alkali metal hydroxides such as sodium or potassium hydroxide and alkali metal carbonates such as sodium or potassium carbonate.

The first condensation is preferably carried out at a temperature of at least 50 ° C, particularly preferably at a temperature of 70 to 180 ° C; the reaction time is between 1 and 20 hours, preferably between 1 and 10 hours. In this condensation, a ketone such as methyl ethyl ketone or methyl isobutyl ketone or a polar aprotic solvent such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, hexamethylphosphoramide or sulfolane may be used as the solvent.

In the second condensation, a suitable reaction temperature lies in the temperature range of 40 to 200 ° C and the reaction time is 0.5 to 10 hours. In this second condensation, a ketone such as methyl ethyl ketone or methyl isobutyl ketone or toluene may be used as the solvent.

In dealkylation, the dealkylating agent is used in an amount equal to 1.5 to 2 molar by the amount of the compound of formula XII.

If pyridine hydrochloride is used as the dealkylating agent, the reaction is preferably carried out at a temperature of 50 to 250 ° C, particularly preferably at a temperature of 130 to 200 ° C and atmospheric pressure for 1 and 10 hours.

When 40-60% by weight of hydrohalic acid, such as hydrobromic acid or hydroiodic acid, is used as the dealkylating agent, the dealkylation reaction is preferably carried out in the presence of a fatty acid solvent having a total carbon number of 1 to 4. , such as in the presence of acetic acid or acetic anhydride, in an amount equal to 1- to 50 volume times the volume of the compound of formula XII for 1 to 10 hours, preferably at atmospheric pressure and at 90 to 150 ° C. Celsius.

Methods for converting the general substituent Z ⁴ in the general formula V to the general substituent Z ¹ in the general formula I will be described below.

1. Preparation of salts

A compound of formula Va,

OCH (CH ₂ ) _and COH (Va.) In which ______

X, Y, R and n are as defined above, neutralized with an alkaline reagent (e.g., sodium hydroxide, potassium hydroxide or ammonia) to form a compound of formula Ic,

in which

X, Y, R and n are as defined above.

2. Preparation of halides

The compound of formula (Va) is reacted with a halogenating agent (such as SOC12, R17, PCl5, POCh and the like) to obtain a compound of formula (Id),

»In which in which

X, Y, · Ran. are as defined above and Z ¹ represents a halogen atom.

3. Preparation of amides

The compound of formula V or the compound of formula Id is aminated with an amine of formula

ZXc — H,

Z * b. represents an amino group, an alkylamino group having 1 to 4 carbon atoms, an alkoxycarbonylmethylamino group wherein the alkoxy group has 1 to 4 carbon atoms, a hydroxycarbonylmethylamino group, an aniline group whose aryl radical may be substituted by 1 to 3 halogen atoms, or pyridine; A 2-ylamino group to form a compound of formula Ie,

in which

X, Y, R, on Z 1 _C are as defined above.

4. Preparation of thioesters

The compound of the formula (Id) is reacted with a mercaptan of the formula: ## STR4 ## in which

ZX _b is C 1 -C 4 alkylthio, C 2 -C 4 alkenylthio or phenylthio whose aryl radical may be substituted by 1 to 3 halogen atoms or C 1 -C 4 alkyl to give a compound of formula (If) ,

in which

X, Y, R, ZX _b are as defined above,

........ ... . . -. ... ; ... ...

5. Preparation of esters (5-1) A compound of formula Va or formula Id is esterified with an alcohol of formula carbon atoms, the cycloalkyl moiety of which may be substituted with an alkyl group. C 1-4 alkoxy, alkoxycarbonylalkoxy, each alkoxy having 1-4 carbon atoms, a phenexyl group whose aryl radical may be substituted with 1-3. halogen atoms or a (C1-C4) alkyl, benzyl or glycidyloxy group;

Ζ4-Η ^, in which to form a compound of formula Ig,

Z ¹ ,. represents an alkoxy group having 1 to 6 carbon atoms, wherein the alkyl radical may be substituted by 1 to 3 halogen atoms, an alkoxyalkoxy group wherein each alkoxy group has 1 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, an alkynyloxy group having 2 to 4 carbon atoms atoms, cycloalkoxy having 3 to 6 carbon atoms

OCH (CHJ _and CZ _e in which

X, Y ,. R 1 and Z ^x c are as defined above.

(5-2) A compound of formula Vb,

OCHÍCH ^ (C-tCl)

alkoxy (Vb) wherein

X, Y,. R and n are as defined above in reaction with a general alcohol. formulas

FOR. -H in which '

¹ Z _e has the abovementioned meaning, in the presence of a catalyst tvořeného- Lewis acid such as boron trifluoride, to form a compound of formula Ig-

6. Preparation of acids

The compound of formula (Vb) is hydrolyzed [e.g. with a suitable acid or base] to form a compound of formula (Va).

For example, the starting compounds of formula II may be a compound of formula IIa,

in which

Y is as defined above and

Y ‘represents a fluorine atom or a chlorine atom, prepared as follows.

2-Amino-5-methylpyridine (described, for example, in Chemical Abstracts, Vol. 43, 7050i [1949]] is diazotized with or without halogenation to form a compound of formula IIb,

in which it means

Y is hydrogen, chlorine or bromine; and

A halogen atom, the preferred halogen atom being a fluorine atom, a chlorine atom and a bromine atom.

The compound of formula IIb is then chlorinated under irradiation with ultraviolet light to form the compound of formula IIc.

in which

Y and Y 'are as hereinbefore defined, which are then reacted with hydrogen fluoride at 0 to 50 ° C or with a metal fluoride such as antimony fluoride at 100 to 250 ° C to form a compound of hydroquinone monoalkyl ether of formula of formula Ha.

Other starting materials, i.e., hydroquinone, ^and hyrrochinodmo noalkylether formula XI P-hydroxyfenoxyalkadkarboxylová acid of the formula X or its derivatives, acid · haloalkanecarboxylic formula VII or. its derivatives and the compound of formula VIII are described in 210604, for example, in U.S. Patent 4,046,553. Trifluoromethylliodide, which is also used as one of the starting materials in the process of the invention, is described, for example, in Org. Reactio-n, Vol. 9, p. 358.

In the following, several examples of the preparation of the herbicidally active compounds of the invention will be given. In these examples, all parts, all percentages, and all ratios are by weight unless otherwise indicated.

Example 1

Preparation of ethyl - {N - [(5-trifluoromethyl-2-pyridyloxy) phenoxy]} opionate (A-1)

(a) 40 ml of dimethyl sulfoxide, 4.2 g of hydroquinone, 5 g of 2-chloro-5-trifluoromethylpyridine and 2.3 g of potassium hydroxide are reacted at 150 ° C for two hours under a nitrogen atmosphere and with stirring. The reaction product is then allowed to cool, and the cooled product is then poured into an appropriate amount of ice-water. The reaction mixture was then neutralized with 30% hydrochloric acid and extracted with methylene chloride.

The extract was then washed with water, dried over anhydrous sodium sulfate, and the methylene chloride was removed by distillation to give 2.5 g of 2- (4-hydroxyphenoxy) -5-trifluoromethylpyridine having a melting point of 82-84 ° C.

(b) 40 ml of dimethyl sulphoxide, 5.0 g of hydroquinone monomethyl ether, 5 g of 2-chloro-5-trifluoromethylpyridine and 2.3 g of potassium hydroxide are reacted at 150 DEG C. for three hours. The reaction product is allowed to cool, then the cooled reaction product is poured into an appropriate amount of ice-water. The mixture is then extracted with methylene chloride and the extract is concentrated in vacuo ^. Wash with water and dry over anhydrous sodium sulfate.

The methylene chloride was then removed by distillation and the resulting residue containing 2- (4-methoxyphenoxy) -5-trifluoromethylpyridine was treated with 5 g of pyridine hydrochloride. The mixture was allowed to react with stirring at 140-160 ° C for two hours. After the reaction mixture had cooled, it was poured into an appropriate amount of ice-water, and the mixture was extracted with methylene chloride.

The methylene chloride layer was then extracted again with 5% aqueous sodium hydroxide solution, and the resulting aqueous extract was acidified with 30% hydrochloric acid to give a solid. The resulting product was isolated by filtration to give 2.1 g of 2- (4-hydroxyphenoxy) -5-trifluoromethylpyridine after drying.

5.1 g of 2- (4-hydroxyphenoxy) -5-trifluoromethylpyridine obtained in steps a) and b) above and 3.6 g of ethyl (ar-bromo) pro28 pionate are dissolved in 50 ml of methyl ethyl ketone, whereupon the solution thus obtained is allowed to react for two hours in the presence

3.3 g of anhydrous potassium carbonate by heating to 80 ° C under reflux. After completion of the reaction, water is added to the reaction product to dissolve any remaining solid; the mixture is then concentrated by distillation under reduced pressure to remove the methyl ethyl ketone.

The residue was then extracted with toluene and the extract was washed with water and dried over anhydrous sodium sulfate. The toluene is then separated by distillation to give an oily product. The resulting oily product is solidified by cooling, washed with n-hexane and dried to give 1.8 g of the desired product, m.p. 63-65 ° C.

(A — 2)

9.1 g of 2-chloro-5-trifluoromethylpyridine and 21 g of ethyl [4- (4-hydroxyphenoxy)] propionate are dissolved in 50 ml of dimethylsulfoxide and the solution thus obtained is reacted for two hours at 150 DEG C. in the presence of 13.8 g of anhydrous potassium carbonate with stirring.

The reaction product is then allowed to cool and the reaction product thus cooled is poured into ice-water and the resulting solid is extracted with toluene. The toluene layer is then washed several times with water, dried over anhydrous sodium sulfate and the toluene is removed by distillation to give

12.4 g of oily substance (i).

The aqueous layer which had been removed by the above toluene extraction was washed with toluene and acidified with 30% hydrochloric acid to give an oil. The resulting oil was then extracted with methylene chloride, washed well with water, and dried over anhydrous sodium sulfate. The methylene chloride was then removed by distillation to give 9 g of an oily substance which was mixed with an excess volume of ethanol.

ml of an ethereal solution of boron trifluoride was added to the above mixture, and the mixture was heated to 80 ° C under reflux for two hours. A small amount of water is then added to the reaction mixture, and the oily phase obtained after distilling off the ethanol is extracted with methylene chloride. The extract was washed with water and dried over anhydrous sodium sulfate, after which methylene chloride was removed by distillation to give 6 g of oily substance (ii).

The oily products (i) and (ii) obtained above were combined and adsorbed on a silica gel column, from which they were then eluted with toluene. Toluene was removed from the resulting eluate by distillation to give 11.6 g of an oily substance; converting the oil into a solid by cooling; The solid obtained is washed with n-hexane and dried to give 6.5 g of the desired product.

(B)

4.1 g of ethyl 1 - {[4- (5-iodo-2-2-pyridyloxy) phenoxy] propionate, 2.45 g of trifluoromethyl iodide, 40 ml of pyridine, and 1.62 g of copper dust are mixed in an autoclave, and then the resulting mixture is allowed to react at 120-130 ° C for 12 hours with stirring. After completion of the reaction, the reaction mixture is allowed to cool, whereupon the copper salt precipitates by addition of diethyl ether; the precipitated salt is removed by filtration.

The resulting ethereal solution was washed successively with water, 15% hydrochloric acid and again with water, and then dried over anhydrous sodium sulfate. The resulting ether solution was then concentrated and the resulting oily substance (5 g) was purified by silica gel column chromatography using methylene chloride as eluent and distilled under reduced pressure to give 1.9 g of the desired product having a melting point of 162-185 ° C. 400 Pa.

Example 2

Preparation of α- [4- (5-Trifluoromethyl-2-pyridyloxy) phenoxy] propionic acid (A) g of 2- (4-hydroxyphenoxy) -5-trifluoromethylpyridine is dissolved in 100 ml of toluene and then treated as follows: the solution obtained, 7 g of sodium hydroxide at 60 ° C and the solution was m ^r cha after a period of 30 minutes. To react with ⁿ e ^{m p} Otom ESI teptotě ^{at 50} to ⁸⁰ ° ^C. was added dropwise 8.8 g O- acid «-chloropropionic and the mixture was stirred for one hour; then 7.6 g of sodium hydroxide are added.

The resulting mixture was then allowed to react for 1 to 1.5 hours by heating to 110 ° C under reflux. Water was added to the resulting reaction product, and the mixture was neutralized with 10% sulfuric acid. The mixture was then allowed to stand at 70 to 80 ° C to separate the organic and aqueous layers.

Water and sodium hydroxide were added to the organic layer with stirring at 70-80 degrees Celsius to adjust the pH of the solution to 9-10. After removal of toluene, the resulting aqueous solution was acidified with 10% sulfuric acid. Toluene (100 ml) was added to the resulting solution, and the mixture was washed with water, dried over anhydrous sodium sulfate, and filtered. The toluene is then removed and the residue is washed with n-hexane to give 16.8 g of the desired product having a melting point of 97-100 ° C.

(B)

3.55 g of ethyl [.alpha .- [4- (5-trifluoromethyl-2 ^- yridyloxy) -phenoxy]} propionate obtained as described in Example 1 (B) are added to a mixture of 4 g of sodium hydroxide, 16 ml. water and 16 ml of ethanol, and the mixture is allowed to react with stirring for two hours at room temperature. Upon completion of the reaction, an appropriate amount of ice-water was added to the reaction mixture, and the mixture was acidified with 30% hydrochloric acid. The crystals formed are filtered off, washed with water and dried to give 2.5 g of the desired product.

Example 3

Preparation of methyl f [4- (5-trifluoromethyl-2-pyridyloxy) phenoxy] propionate (A)

255 g of 2- (4-hydroxyphenoxy) -5-trifluoromethylpyridine, 199.1 g of methyl [α-bromo] propionate and 207 g of anhydrous potassium carbonate are left to react for 2 hours by heating to 80 ° C under reflux. condenser in 1000 ml of methyl ethyl ketone. After cooling the reaction mixture, any precipitated inorganic salt was removed by filtration and the methyl ethyl ketone was distilled off. The residue was extracted with methylene chloride and the extract was ROMs ^{p p p} Ostu ^some waterproof ^ ^d 5% of sodium bicarbonate Nym sodnéhoa again with water.

The resulting extract was then dried over anhydrous sodium sulfate and the methylene chloride was removed by distillation to give 346 g of an oil which was then rapidly cooled to give a solid. The resulting solid product is then washed with n-hexane and recrystallized from ethanol to give 196 g of the desired product, having a melting point of 72-74 ° C.

[B]

3.27 g of α- [4- [5-trifluoromethyl-2-pyridyloxy) phenoxy] propionic acid prepared according to Example 2 (B) are dissolved in 33 ml of methanol, and 0.5 g of diethyl ether solution is added thereto. boron trifluoride and the resulting mixture was allowed to react for 3 hours by heating to 64 ° C under reflux. After completion of the reaction, a small amount of water was added to the reaction mixture, and the resulting mixture was concentrated under reduced pressure and extracted with methylene chloride.

The extract was washed with water and dried over anhydrous sodium sulfate. The methylene chloride is removed by distillation and the residue is evaporated under reduced pressure to give 2.3 g of the desired product in oily form, having a boiling point of 175-177 ° C / 2 mm Hg. O210604 oil obtained is removed to obtain a solid product having a melting point of 72-74 ^o C.

Example 4

Preparation of sodium [4- (5-trifluoromethyl-2-pyridyloxy) phenoxy] propionate

3.27 g of [4- (54-trifluoromethyl-2-pyridyloxy) phenoxy] propionic acid are dissolved in a small amount of ethanol, and the solution thus obtained is mixed with 0.8 g of a 50% aqueous sodium hydroxide solution. The mixture is concentrated under reduced pressure and the precipitated crystals are then dried to give 3 g of the desired product, having a melting point of 70-75 ° C.

Example 5

Preparation of methyl .alpha .- [443-chloro-5-trifluoromethyl-2-pyridyl) phenoxy] propionate (A-1) g 2,3-dichloro-5-trifluoromethylpyridine, 40 ml dimethylsulfoxide, 4.2 g of hydroquinone and 2.3 g of potassium hydroxide were allowed to react at 150 ° C for two hours with stirring below. The reaction mixture was then allowed to cool, and the cooled reaction mixture was then poured into an appropriate amount of ice-water. The resulting mixture was neutralized with 30% ^{for y} ~ | Lina HCl and extracted with methylene chloride ж. No.

The extract was washed with water, dried over anhydrous sodium sulfate and the methylene chloride was removed by distillation to give 2.7 g.

2- (4-hydroxyphenoxy) -3-chloro-5-trifluoromethylpyridine having a melting point of 70-72 ° C.

5.8 g of the resulting 2- (4-hydroxyphenoxy) -3-chloro-5-trifluoromethylpyridine and 3.3 g of methyl (.beta.-bromopropionate) are dissolved in 50 ml of methyl ethyl ketone and the resulting mixture is reacted by heating to 80 DEG. ° C under reflux for two hours in the presence of 3.3 g of anhydrous potassium carbonate, water is added to the reaction mixture, and the mixture is concentrated under reduced pressure to distill off the methyl ethyl ketone.

The residue was extracted with toluene and the extract was washed with water, dried over anhydrous sodium sulfate and the toluene was removed by distillation to give an oil. The resulting oily product is solidified by cooling; the solid product is washed with n-hexane and dried to give 2.2 g of the desired product having a melting point of 67-69 ° C.

(A — 2)

4.3 g of 2,2-dichloro-5-trifluoromethylpyridine and 4 g of methyl [- (4-hydroxyphenoxy)] propionate are dissolved in 30 ml of dimethylsulfoxide and the resulting solution is reacted by heating to 150 ° C for a period of time. two hours in the presence of 3.3 g of anhydrous potassium carbonate with stirring. After cooling the reaction mixture, the cooled mixture was poured into ice-water and the resulting solid was extracted with toluene.

The toluene layer was washed several times with water, dried over anhydrous sodium sulfate, and toluene was removed by distillation to give

3.5 g of oily product (iii).

The aqueous layer obtained during the toluene extraction was washed with toluene and acidified with 30% hydrochloric acid to give an oily product. The oily product obtained is extracted with methylene chloride and the extract is washed with water and dried over anhydrous sodium sulfate.

The methylene chloride was then removed from the extract to give 1.5 g of an oily product. This product was mixed with an excess of methanol by volume, and 2 ml of diethyl ether boron trifluoride solution was added thereto, and the mixture was heated to 64 ° C under reflux for <2 hours. A small amount of water is then added to the reaction mixture and methanol is removed by distillation to give an oily product.

The resulting oily product was extracted with methylene chloride and the extract thus obtained was washed with water, dried over anhydrous sodium sulfate and the methylene chloride was removed by distillation to give 1.2 g of oily product (iv).

The combined oily products (iii) and (iv) are adsorbed onto a silica gel chromatography column and then eluted with toluene. Toluene was removed from the resulting eluate to give 2.5 g of an oily product. The product is converted to a solid by cooling; the solid product is then washed with n-hexane and dried to give 2.1 g of the desired product.

(B)

3.9 g of methyl [α - [(3-chloro-5-iodo-2-pyridyloxy) -phenoxy] -propionate, 2.45 g of trifluoromethyl iodide, 40 ml of pyridine and 1.62 g of copper dust are mixed in an autoclave and the resulting mixture was allowed to react with stirring at 140 ° C for two hours, after which the reaction mixture was maintained at 160-170 ° C for one hour.

After the reaction mixture had cooled, diethyl ether was added thereto, and the precipitated copper salts were removed by filtration. The etherate filtrate was washed successively with water, 10% hydrochloric acid and again with water, and then dried over anhydrous sodium sulfate. The ether solution was concentrated to give 1.5 g of an oily product which was then purified by silica gel column chromatography then eluted with methylene chloride; from the eluate the solvent was removed by distillation to give 500 mg of the desired product.

Example 6

Preparation of γ- [4- (5-Trifluoromethyl-2-pyridyloxyphenoxy) valeric acid

A 50% aqueous solution of sodium hydroxide [1.8 g] and 20 ml of toluene were added to 10 g of 2- (4-hydroxyphenoxy) -5-trifluoromethylpyridine, followed by stirring for 10 minutes. From this mixture. The toluene is then removed by azeotropic distillation in admixture with water. 20 grams are then added to the resulting mixture. of γ-valerolaikton and the resulting mixture was reacted with stirring at 170-180 ° C for 5 hours. After completion of the reaction, the reaction mixture was poured into water and acidified with 30% hydrochloric acid to precipitate a solid.

The resulting solid was extracted with 20 ml of methylene chloride and the extract was washed with water, dried over anhydrous sodium sulfate, filtered and the solvent removed by distillation to give 4 g of the desired product, m.p. 231-235 ° C.

Example 7

Preparation of Ethyl [γ- [4- (5-trifluoromethyl-2-pyridyloxy) phenoxy] valerate ⁴⁰ g of γ 44- (5-trifluoromethyl-2-pyridyloxy) phenoxy] valeric acid are dissolved in 10 ml of ethanol and the solution thus obtained is dissolved. 0.5 ml of diethyl ether solution of boron trifluoride was added and the mixture was allowed to react for 3 hours at 78 ° C under reflux, then allowed to cool, and then 10 ml of methylene chloride was added to the cooled reaction mixture. and washed several times with water.

The methylene chloride layer is dried over anhydrous sodium sulfate, filtered and the methylene chloride is removed from the filtrate by distillation to give 4.1 g of the desired product, boiling 150-153 ° C / 1 mm Hg.

Example 8

Preparation of α- [4- (5-trifluoromethyl-2-pyridyloxy) phenoxy] propionanilide g o- [4- (5-trifluoromethyl-11-pyridopyloxy) -1-phenoxy] propionyl chloride, prepared from

- [4- (5-Trifluoromethyl-4-pyridyloxy) phenoxy] propionic acid and thionyl chloride in a manner known per se, and 1.3 g of aniline are dissolved in 10 ml of benzene, followed by the dropwise addition of 1. 2 g of pyridine.

The mixture was then heated to 80 DEG C. for 3 hours and the reaction product was washed several times with 20 ml of water. The benzene layer was separated, dried over anhydrous sodium sulfate, and filtered. The benzene is then removed by distillation to give 4.3 g of the desired product having a melting point of 139-141 degrees Celsius.

The herbicidally active compound of the invention may be dispersed in water to obtain a water dispersion. The herbicidally active compound may also be formulated in various other conventional forms, such as an emulsifiable concentrate, a wettable powder, a water-miscible solution, a dusting agent or a granulate.

In addition to the herbicidally active substance, those formulations may also contain the usual agriculturally acceptable ingredients such as:

carriers such as diatomaceous earth, calcium hydroxide,. calcium carbonate, talc, bone meal, kaolin, bentonlt, or Jeeklite (a trade name of kaolinite manufactured by Jeeklite Co.);

solvents such as n-hexane, toluene, xylene, solvent naphtha, ethanol, dioxane, acetone, isophorone, methyl isobutyl ketone, dimethylformamide, dimethylsulfoxide or water;

or anionic or nonionic surfactants such as sodium alkylsulfate, sodium alkylbenzenesulfonate, sodium lignin sulfonate, rlyoxyethylenlaulyl ether,. a polyoxyethylene fatty acid ester or a poly (Y ⁶ ') ethylene sorbitan fatty acid ester.

A suitable ratio of the herbicidally active compound according to the invention to said additives is in the formulations 1 to 90: 99 to 10, preferably 1 to 70: 99 to 30.

The herbicidal composition of the invention may also be mixed with other suitable agricultural chemicals, such as other herbicidal, insecticidal and fungicidal agents, as well as other agricultural products, such as fertilizers, soil modifiers, soil or sand, which may be This is done during formulation or during the actual application of the herbicidal composition of the invention. Often, such a combination also produces a combination effect.

In the following, several examples of preparation of herbicidal formulations containing the herbicidally active compound of the invention will be given.

Example 9

In order to obtain an emulsifiable concentrate:

parts of ethylfce- [4- (5-trifluoromethyl-2-pyridyloxy) phenoxy] propionate, parts of xylene and parts of Sorpol 2806B (trade name of a mixture of polyoxyethylenephenylphenol derivative, polyoxyethylene alkyl aryl ether, polyoxyethylene sorbitan alkyl alkylate and alkylarylsulfonate, manufactured by Toho Chemical Co.) as a surfactant.

Example 10

In order to obtain an emulsifiable concentrate:

parts of ethyl [4- (5-trifluoromethyl-2-pyridyl) phenoxy] jvalerate, parts of xylene and parts of polyoxyethylene stearate.

Example 11

It is mixed:

parts of bentonite, parts of Jeeklite, and parts of sodium lignin phosphonate, whereupon the mixture is granulated. To prepare the herbicidal composition in the form of a granulate, the granules obtained in this way are sprayed with a solution prepared by diluting 7 parts of allyl- [4- (5-trifluoromethyl-2-pyridyloxy) phenoxy] propionate with acetone.

Example 1 a d 12

In order to obtain a wettable powder, it is homogeneously mixed and ground to a powder:

parts of N- (pyridin-2-yl) -α- [4- (5-trifluoromethyl-2-pyridyloxy] phenoxy] propionamide; parts of Jeeklite;

Example 13

To obtain a wettable powder, mix:

parts of Jeeklite, parts of bone meal, parts of Lavelin S (trade name of sodium naphthalenesulfonate · formaldehyde condensate, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and parts of Sorpol 5039 (trade name for polyoxyethylene alkylarylether sulfate, manufactured by Toho Chemical, Co., Ltd.).

The mixture was then treated with methyl 4 - [4- (3-chloro-5-trifluoromethyl-2-pyridyloxy) phenoxy]} propionate in a 4: 1 ratio.

Example 14

To obtain a water-miscible solution, mix:

parts of sodium α- [4- (5-trifluoromethylpyridyloxy) phenoxy] propionate, parts of polyethylene glycoloctylphenyl ether, parts of sodium dodecylbenzenesulfonate, and parts of water.

In the following, the unique herbicidal activity of the herb will be described in more detail

of a bicidal composition of the invention.

1) The herbicidally active compound can be used to control grass weeds by pre-emergence soil application or foliar application during unwanted weed growth. In particular, the herbicidally active compound according to the invention can be used for controlling weed weeds which have already reached a height of about one meter by foliar spraying.

Since the herbicidally active compound of the invention is extremely nontoxic to broad-grown crops such as soya, groundnuts and cotton, this compound is suitable for the selective control of weeds on alpine farms.

2) When the method of application, the dose and the time of application are appropriately selected, for example, when the weeds grow together with crops such as corn and the like, and are subjected to a low-dose foliar application (5 to 20). g / 100 m ² ) of the active compound according to the invention after the crop has grown to a certain degree, the heribicidally active compound according to the invention can be applied to a field where grass crops are grown.

Also, when the dose of the herbicidally active compound is appropriately increased or the compound of the invention is used in admixture with other herbicides, weeds other than grass weeds can also be controlled.

3) The herbicidally active compound according to the invention has only a very low toxicity to fish and therefore does not have a detrimental effect on water management.

The herbicidally active compounds according to the invention are preferably applied in higher-lying farms, in particular in farms where broad-leaved crop plants are grown; said herbicidally active substance can also be applied in orchards, forests and in various non-agricultural parcels.

The herbicidally active compound of the invention may be applied by soil or foil210604

Application in high-rise farms or irrigation conditions.

The appropriate application rate depends on various factors, such as climatic and soil conditions, the type of drug formulation, the time and method of application, and the type of crop and weeds to which the herbicidally active agent is applied.

When the herbicidally active compound according to the invention is used in the form of a solid composition (such as in the form of a dust or granulate), the amount of active compound is 0.01 to 100 kg / ha, preferably 0.05 to 50 kg / ha, and particularly preferably 0.1 to 25 kg / ha.

In the following, the herbicidal activity of the herbicidal active ingredients of the herbicidal compositions of the present invention will be demonstrated in tests.

Example 15 Land imitating the conditions of higher land. A predetermined amount of seeds of cultivated edible hedgehogs of chicken feet (JJKN), radish (R) and soybean (S) are sown in the soil and then covered with soil containing grass weed seeds such as Digitaria adscendens, I1ENR., Echinochloa crus-galli REAUV and Setaria viridis BEAUV, about 1 cm thick, two days after sowing, the pans were sprinkled with aqueous dispersions of each of the herbicidal compounds listed in Table 1, and the weed growth was evaluated visually after a further 30 days. The degree of growth inhibition is evaluated according to a ten-degree scale, where score 10 means total growth inhibition and score 1 means no effect on growth.

Pour over 1/30 m ² flat bowls

Table 1 Compound number Amount of active substance (kg / ha) Degree of growth inhibition JJKN R with ¹ Travinovitý weed 1 5 8 1 1 10 2.5 7 1 1 9 2 5 10 1 1 10 2.5 10 1 1 10 3 5 10 1 1 10 2.5 10 1 1 10 4 5 10 1 1 10 2.5 10 1 1 10 5 5 10 1 1 10 2.5 10 1 1 10 6 5 10 1 1 10 2.5 10 1 1 10 7 5 10 1 1 10 2.5 10 1 1 10 9 5 10 1 1 10 2.5 10 1 1 10 10 5 10 1 1 10 2.5 10 1 1 10 11 5 8 1 1 10 2.5 7 1 1 9 12 5 10 1 1 10 2.5 10 1 1 10 13 5 10 1 1 10 2.5 10 1 1 10 14 5 10 1 1 10 2.5 10 1 1 10 15 Dec 5 10 <1 1 10 2.5 10 1 1 10 16 5 10 1 1 10 2.5 10 1 1 10 17 5 10 1 1 10 2.5 10 1 1 10 18 5 10 2 1 10 2.5 10 1 1 10 19 Dec 5 10 1 1 10 2.5 10 1 1 10 20 May 5 10 1 1 10 2.5 10 1 1 10

Compound Quantity Degree Inhibition of Growth

number active substances (kg / ha) JJKN R S Grassy weeds 21 5 10 1 1 10 2.5 10 1 1 10 22nd 5 10 1 1 10 2.5 10 1 1 10 23 5 10 1 1 10 2.5 10 1 1 10 24 5 . 10 1 1 10 2.5 10 1 1 10 25 5 10 1 1 10 2.5 10 1 1 10 26 5 10 1 1 10 2.5 10 1 1 10 27 Mar: 5 10 1 1 10 2.5 10 1 1 10 2) 8 5 10 1 1 10 2.5 10 1 1 10 29 5 10 1 1 10 2.5 10 1 1 10 30 5 10 1 1 10 2.5 10 1 1 10 31 5 10 1 1 10 2.5 10 1 1 10 32 5 10 1 1 10 2.5 10 1 1 10 33 5 10 1 1 10 2.5 10 1 1 10 34 5 10 1 1 10 2.5 10 1 1 10 35 5 10 1 1 10 2.5 10 1 1 10 36 5 10 1 1 10 2.5 10 1 1 10 37 5 10 1 1 10 2.5 10 1 1 10 38 5 10 1 1 10 2.5 10 1 1 10 39 5 10 1 1 10 2.5 10 1 1 10 40 5 10 1 1 10 2.5 10 1 1 10 43 5 10 1 1 10 2.5 10 1 1 10 44 5 10 1 1 10 2.5 10 1 1 10 45 5 10 1 1 10 2.5 10 1 1 10 46 5 10 1 1 10 2.5 10 1 1 10 47 5 10 1 1 10 2.5 9 1 1 9 48 5 10 1 1 10 2.5 9 1 1 9 49 5 10 1 1 10 2.5 10 1 1 10 50 5 10 1 1 10 2.5 10 1 1 10 51 5 10 1 1 10 2.5 10 1 1 10 52 5 10 1 1 10 2.5 10 1 1 10 53 5 9 1 1 9 2.5 8 1 1 8 54 5 10 1 1 10 2.5 10 1 1 10

210604 39 40 Degree of growth inhibition Grassy weeds Compound number Amount of active substance (kg / ha) JJKN R WITH 55 5 10 1. 1 10 2.5 10 1 1 10 56 5 10 1 1 10 2.5 10 1 1 10 57 5 10 1. 1 10 2.5 10 1 1 10 58 5 10 1 1 10 2.5 10 1 1 10 59 5 10 1 1 10 2.5 10 1 1 10 60 5 10 1. 1 10 2.5 10 1. 1 10 61 5 10 1 1 10 2.5 10 1 1 10 62 5 10 1 1 10 2.5 10 1 1 10 63 5 10 1 1 10 2.5 10 1 1 10

Example 16

On flat flats with an area of 1/30 m ² , the soil imitating the conditions of the above ground is poured and the cultivated edible piglets corn and soybean are sown in this soil. The tactp-treated soil is then covered with an approximately 1 cm thick layer of soil. When the hedgehog reaches the 2.5-leaf stage, a predetermined amount of the aqueous dispersion of each of the herbicidally active compounds listed in Table 2 is applied to the foliage. Twenty days after the dispersion is applied, the growth status of the hedgehog and soybean is visually assessed. The same classification system as in the preceding embodiment is used. The results obtained are summarized in Table 2 below.

Table 2 .....

Compound No. Concentration Degree of growth inhibition

active substances (ppm) JJKN Soya 2 400 10 1. 200 10 1 3 400 10 1 200 10 2 9 400 10 1 200 10 1 10 400 1.0 1 200 10 1 12 400 10 1 200 10 1 13 400 10 1 200 10 1 15 Dec 400 10 1 200 10 1 16 400 10 1 200 10 1 17 400 10 1 200 10 1 18 400 10 1 200 10 1 21 400 10 1 200 10. 1 25 400 10. 1 200 10. 1 26 400 10. 1 200 10. 1 27 Mar: 400 10. 1 200 10 · 1

Compound number Active substance concentration (ppm) Degree of growth inhibition JJKN Soya 32 400 10. 1 200 10 · 1 37 400 10 1 200 10 1 58 . 400 10 · 1 200 10 1 59 400 10 1 200 10 1

Example 17

The predetermined quantity of cotton seeds is planted in pots with a cross section equal to 1/50 m ² . When the cotton reaches the fourth leaf stage, the pots are sprinkled with a predetermined amount of the aqueous dispersion of each of the compounds listed in Table 3. Twenty days after the dispersion is applied, the growth status of the cotton is evaluated visually to determine the degree of phytotoxicity. The degree of phytotoxicity is evaluated in the following stages: necrosis, restricted growth and growth inhibition, and the results obtained are shown in Table 3. The degree of phytotoxicity was determined according to a 10-degree scale in which grade 10 means that cotton has completely withered and grade 1 means Growth similar to growth on a plot where the herbicidally active substance has not been applied.

Table 3

Test compound

Amount of active substance ( ^k g ^/ ha)

Necrosis

Phytotoxicity

Wilting

Growth inhibition

Compound No. 12

7¾

OCHCOCÍI 11

OCHCOCJ + (2) (2)

(3) (1) Compound from the US patent (2) Compound from the German specification (3) Compound from U / N-Kiitnit

954 442 of the file

DOS 2 433 067, file 4,046,553

Example 18

A grassy plant of the species Agropyrum repens, obtained by dividing the mother tuft of about 10 cm in diameter into two parts, se. plant in two pots. with a cross-section of 1/50 m · ^{1 2} (each part into one pot). When said grass reaches the 4.5 leaf stage (50 to 60 stems) and has a height of about 25 to 30 cm, each pot is sprinkled with a predetermined amount of water dispersion of each of the compounds listed in Table 4 below.

Fifty days after said dispersion application, the degree of grass recovery is evaluated. The results obtained are shown in Table 4 below; this level of regeneration is evaluated on a six-step scale, where mark 5 means that grass regeneration is completely controlled, and mark 0 means that regeneration is not inhibited and growth is similar to growth on a plot on which no herbicide has been applied.

Table 4

Test compound

Amount of active substance (kg / ha) Degree of inhibition of regeneration

Compound No. 56 0.125 0.5 1

ch

I ⁰

OCHCON (1)

Cl

Cl

I ^J O

I č

-OCHCON (2)

0.125

0.5

0.125

0.5 (1) Compound from German Patent Specification 2,443,067.

(2) Compound of U.S. Pat. No. 4,046,553.

Example 19

The two underground stems (10-20 cm long) of the plant Sorghum halepence (L.) Pers., Containing 4 to 5 nodes, are transplanted into pots with a cross-section of 1/50 m ² (each stalk into one pot). When the plant reaches the 4-5 leaf stage, the pots are sprayed with an aqueous dispersion of each of the compounds listed in the following Table 5. About forty. days after application. the number of regenerated plants is determined by the dispersion. The results obtained are summarized in Table 5 below.

Table 5

Test compound

Amount of active substance (kg / ha) Number of regenerated plants

Compound No. 12

9¾ o

I II

OCHCOCH ^

0.125

0.25

0.5

0.125

0.25

0,5 [1]

0.125

0.25

0,5 mm (2)

Test compound The amount of active ingredient (kg / ha) Number of regenerated plants ^C 3 ^H 0.1253 _N / - \ \ ct 0.251 -yo it У о - / ОУ- о снсо с н _{2 £} °> ^{50 Ν} (3)

Control Experiment 13 (1) Compound of U.S. Pat. No. 3,954,442.

(2) Compound from German Patent Specification No. 2,433,067.

(3) Compound of U.S. Pat. No. 4,046,553.

It goes without saying that various modifications of the measures of the invention are possible without departing from the scope of the invention, which is clearly defined by the definition of the subject matter of the invention.

Claims (20)

SUBJECT OF THE INVENTION A herbicidal composition comprising a herbicidally effective amount of at least one compound of formula (I) in which: X is fluorine or chlorine, Y is hydrogen or chlorine, n is 0 or 2, R is a hydrogen atom, a methyl or ethyl group, a ^1- hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, the alkyl residue of which may be substituted by 1 to 3 halogen atoms, an alkoxyalkoxy group, each alkoxy group having 1 to 4 carbon atoms atoms, C 2 -C 4 alkenyloxy, C 2 -C 4 alkynyloxy, C 3 -C 6 cycloalkoxy whose cycloalkyl radical may be substituted by C 1 -C 4 alkyl, alkoxycarbonylalkoxy, each alkoxy group 1-4 carbon atoms, phenoxy, the aryl radical of which may be substituted by 1-3 halogen atoms or C1-4 alkyl, benzyloxy, glycidyloxy, C1-4 alkylthio, C2-4 alkenylthio, phenylthio , the aryl radical of which may be substituted (C 1 -C 3) alkyl or (C 1 -C 4) alkyl, amino, (C 1 -C 4) alkylamino, alkoxycarbonylmethylamino (C 1 -C 4) alkoxy, hydroxycarbonylmethylamino (anilino) group; I <4 (I) whose aryl radical may be substituted by 1 to 3 halogen atoms, a pyridin-2-ylamino group, an -O-cation or a halogen atom, and an agriculturally acceptable additive. 2. A herbicidal composition as claimed in claim 1, comprising a herbicidally effective amount of at least one compound of formula (I) in which: X is fluorine, Y is hydrogen or chlorine, R is methyl, n O, Z ¹ hydroxyl, alkoxy of 1 to 6 carbon atoms, the alkyl radical of which may be substituted by 1 to 3 halogen atoms, alkoxyalkoxy, where each alkoxy group has 1 to 4 carbon atoms, alkenyloxy of 2 to 4 carbon atoms, alkynyloxy (C 2 -C 4) -cycloalkoxy, the C 3 -C 6 -cycloalkoxy group of which the cycloalkyl radical may be substituted by a C 1 -C 4 alkyl group, the phenoxy group whose aryl radical may be substituted by 1 to 3 halogen atoms, or a C 1 -C 3 alkyl group C 4 -C 4 alkyl, benzyloxy, glycidyloxy or -O-cation. 3. A herbicidal composition as claimed in claim 2, comprising a herbicidally effective amount of at least one compound of formula (I) in which: X is fluorine, Y is hydrogen or chlorine, R is methyl, n O, Z ¹ represents a hydroxyl group, a C 1 -C 4 alkoxy group, a C 2 -C 4 alkenyloxy group, a C 3 -C 6 cycloalkoxy group or an -O-cation. 4. A herbicidal composition as claimed in claim 2, comprising a herbicidally effective amount of at least one compound of formula (I): X is fluorine, Y is hydrogen or chlorine, R is methyl, n O, Z 1 is a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, or -O-cationic. and 5. A herbicidal composition as claimed in claim 2, comprising a herbicidally effective amount of at least one compound of formula (I): X is fluorine, Y is hydrogen or chlorine, R is methyl, n O, Z 1 is a hydroxyl group. 6. A herbicidal composition as claimed in claim 2, comprising a herbicidally effective amount of at least one compound of formula (I): X is fluorine, Y is hydrogen or chlorine; _X R is methyl, n is 0; Z 1 is an alkoxy group having 1 to 4 carbon atoms. 7. A herbicidal composition as claimed in claim 2, comprising a herbicidally effective amount of at least one compound of formula (I): X is fluorine, Y is hydrogen or chlorine, R is methyl, n O, Z1 -O-cation. 8. A herbicidal composition as claimed in claim 1, comprising a herbicidally effective amount of α- [4- (5-trifluoro, methyl-2-pyridyloxy) phenoxy] propionic acid. 9. A herbicidal composition according to claim 1, characterized in that it comprises a herbicidally effective amount of TF acid 4- (3-chloro-5-trifluoromethyl-1 ^ 2 ^ - ^] ^{^,} y idyloxy) phenoxy] propionic acid. 10. A herbicidal composition according to claim 1 comprising a herbicidally effective amount of sodium [alpha] - [4- [5-trifluoromethyl-2-pyridyloxy] phenoxy] propionate. 11. A herbicidal composition according to claim 1, comprising a herbicidally effective amount of sodium [alpha] - [4- [3] Chloro] 5] trifluoromethyl-2-pyridyloxy) phenoxy] propionate. 12. The herbicidal composition of claim 1, comprising a herbicidally effective amount of methyl .alpha .- [4- [5-trifluoromethyl-2-pyridyloxy] phenoxy] propionate. 13. A herbicidal composition according to claim 1 comprising a herbicidally effective amount of methyl-o-n-chloro-5-trifluoromethyl-2-pyridyloxyphenoxy] propionate. 14. A herbicidal composition according to claim 1 comprising a herbicidally effective amount of ethyl .alpha .- [4- [S-trifluoromethyl-4-pyridyloxyphenoxy] propionate. 15. A herbicidal composition according to claim 1 comprising a herbicidally effective amount of ethyl [alpha] - [4] [3] Chloro] 5] trifluoromethyl-2-pyridyloxy) phenoxy] propionate. 16. A method of preparation effective. the substances according to point 1 of the general formula I,. C. YX-Y-O (I) in which is X is fluorine or chlorine, Y is hydrogen or chlorine, R is hydrogen, methyl or ethyl, n 0 or 2 Z 1 is a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, the alkyl radical of which may be substituted by 1 to 3 halogen atoms, an alkoxyalkoxy group wherein each alkoxy group has 1 to 4 carbon atoms, alkenyloxy of 2 to 4 carbon atoms, alkynyloxy of 2 C 3 -C 6 cycloalkoxy, the cycloalkyl radical of which may be substituted by C 1 -C 4 alkyl, alkoxycarbonylalkoxy, each alkoxy having 1 to 4 carbon atoms, phenoxy, the aryl radical of which may be substituted by C 1 -C 4 -alkyl; be substituted with 1 to 3 halogen atoms or a (C1-C4) alkyl group, benzyloxy, glycidyloxy, (C1-C4) alkylthio, (C2-C4) alkenylthio, phenylthio, the aryl of which may be substituted with 1 to 4 carbon atoms 3 halogen atoms or an alkyl group C 1 -C 4, amino, C 1 -C 4 alkylamino, alkoxycarbonylmethylamino wherein the C 1 -C 4 alkoxy, hydroxycarbonylmethylamino, aniline group whose aryl radical may be substituted by 1 to 3 halogen atoms, pyridin-2-ylamino, -O-cation or halogen, characterized in that the 2-halo-5-fluoromethylpyridine of the formula II is first condensed, Y in which Hal means a halogen atom, X and Y are as defined above, and a substituted phenol of formula III, HO-Q (f11) wherein Q represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms or a group RO —OCHfCHzbCZ ⁴ , in which R, n are as defined above and Z ⁴ represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an amino group, in the presence of an alkali to form a substituted pyridylphenyl ether of formula IV, wherein: X, Y and Q are as defined above, where Q is other than a group RO-OCH ² CH ² LCZ ⁴ condenses a substituted pyridyl phenyl ether of formula IV and a haloalkanecarboxylic acid or a derivative of formula VII, R O Hal-CH (CH2bCZ ⁴ (VII) in which Hal, R to Z ⁴ are as defined above, or χ-Valerolaktou in the presence of alkali to give a compound of formula V (V) wherein X, Y, R, to Z ⁴ are as defined above, or salts thereof, optionally converting the Z ⁴ residue of a compound of formula V to the Z ¹ residue, wherein Z ¹ is as defined above, by the method of neutralization, halogenation, amination a thioesterification, esterification or reesterification reaction. 17. The process of claim 16, wherein the 2-halo-5-fluoromethylpyridine of formula (II) is condensed, Hal, X and Y are as defined in 16, with p-hydroxyphenoxyalkanecarboxylic acid or a derivative thereof having the general formula X, in which: R to Z ⁴ are defined as in point of 16 in the presence of an alkaline substance at a temperature at least 50 ° C for 1-20 hours to give compound of formula V, 20 hours to provide a substituted pyridyl-p-hydroxyphenyl ether of formula VI, (V) wherein: X, Y, R, n 'and Z' ¹ have the meaning as in point 16, whereupon optionally converting the residue Z ^{4 of the} compound of formula V to the residue Z ¹ , wherein Z ¹ is as defined in point 16, by a method of neutralization, halogenation, amination, thioasterification, esterification or reesterification reaction. A process according to claim 16, characterized in that the 2-halo-5-fluoromethylpyridine of the formula (II) is condensed in which: Hal, X and Y are as in 16, with hydroquinone in the presence of an alkali at a temperature of at least 50 ° C for 1 to (VI) in which X and Y are as in point 16, whereupon the compound of formula VI is condensed with a haloalkanecarboxylic acid or a derivative of formula VII, R O Hal - CH (CH 2) _n CZ ⁴ (VII) wherein Hal, R to Z ⁴ are as described in paragraph 16, or χ-valerolactone in the presence of an alkaline substance at a temperature of 40-200 ° C for 0.5 to 10 hours to form a compound of formula V in which X, Y, R, to Z ⁴ are as defined in point 16, whereupon optionally, the Z ⁴ residue of the compound of formula V is converted to a residue of Z ¹ as defined in point 16 by the neutralization, halogenation, amination, thioesterification, esterification and reesterification reaction. 19. A process according to claim 16, wherein the 2-halo-5-fluoromethyl-pyridine of formula (II) is condensed in which: Hal, X and Y are as defined in point 16, with a hydroquinone monoalkyl ether of the general Formula XI in which "alkyl" is an alkyl group having 1 to 6 carbon atoms, in the presence of an alkali at a temperature of at least 50 ° C for 1 to 6 20 hours to form a substituted pyridyl-p-alkoxyphenyl ether of formula XII, (II) wherein "alkyl" is as defined above, and X and Y are as in point 16, whereupon the compound of formula XII is dealkylated to give a substituted pyridyl-p-hydroxyphenyl ether of formula VI wherein: X and Y are as in point 16, and the compound of formula (VI) is then condensed with a haloalkanecarboxylic acid or derivative of formula (VII), R O I II Hal-CH (CH] _n GB ⁴ (VII) in which Hal, R to Z ⁴ are as defined in paragraph 16, or with y-valerolactone in the presence of an alkaline substance at a temperature of 40-200 ° C for 0.5 to 10 hours give aa compound of formula V, (VI) R OCH (V) in the river X, Y, R, to Z ⁴ are as defined in point 16, whereupon optionally the Z ⁴ residue of the compound of formula V is converted to a residue of Z ¹ , wherein Z ¹ is as defined in point 16, by neutralization, halogenation, amination, thiesterification, esterification or re-esterification reaction. 20. A process according to claim 16, wherein the alkali metal hydroxide or alkali metal carbonate is used as the alkali in the first and second condensations.