DD283757A5 - HERBICIDES AND METHOD FOR PRODUCING HALOGEN-SUBSTITUTED PHENOXYBENZYL (THI) OL DERIVATIVES - Google Patents

Abstract

The invention relates to herbicidal compositions containing as active ingredients halogen-substituted phenoxybenzyl (thi) ol derivatives of the general formula * in which the substituents R 1 to R 5, X, Y and Z have the meaning given in the description, in addition to extenders and / or surface-active substances , and process for the preparation of the active ingredients. Formula (I) {agent herbicidal; Phenoxybenzyl (thi) ol derivatives; halogen-substituted}

Description

Herbicidal agents and processes for the preparation of halogen substituted phenoxybenzyl (thi) ol derivatives

Field of application of the invention

The invention relates to herbicidal compositions and to processes for preparing the active compounds. The herbicidal compositions according to the invention are used for controlling weeds.

Characteristic of the known state of the art

It is already known "that certain phenoxybenzoic acid derivatives" such as, for example, methyl 3- (2,4-dichlorophenoxy) -6-nitrobenzoate (Bifenox) are herbicidally active (compare US Pat. No. 3,652,645 and U.S. Patent 3,776,715). However, the effect of these known compounds is not always satisfactory.

Object of the invention

The invention provides herbicidal compositions "containing the novel halogen-substituted phenoxybenzyl (thi) ol-derivatives and having excellent herbicidal properties." In particular, they are suitable for the selective control of dicotyledonous weeds in monocotyledonous crops.

Explanation of the essence of the invention

The present invention is based on the object "new active ingredients" which are used to prepare herbicidal compositions.

ι ί

are suitable to "locate" and to provide processes for their production.

According to the invention herbicidal agents "the new halogen-substituted phenoxybenzyl (thi) ol-Oerivate the general formula (I)

R ² R ¹ OH ₂ -YZ

in which 5

R ^{1 represents} hydrogen, halogen, cyano or trifluoromethyl,

R ^{2 is} hydrogen or halogen, 10

R ^{3 is} halogen, cyano, trifluoromethyl, trifluoromethoxy or trifluoromethylsulfonyl,

R ^{4 is} hydrogen or halogen, 15

R ^{5 is} hydrogen or halogen,

- with the proviso that at least two of the substituents

R ¹ , R ² , R ⁴ and R ⁵ are different from hydrogen 20

X is halogen, Y is oxygen, sulfur, sulfinyl or sulfonyl

stands and 25

Z is hydrogen, optionally cyano,

Halo, hydroxy, alkoxy, alkylthio, carboxy, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonylalkoxycarbonyl-substituted alkyl, the in each case optionally substituted by halogen and / or alkyl-substituted cycloalkyl or cycloalkylalkyl, in each case optionally halogen-substituted alkenyl or alkynyl, or represents one of the following groups

Le a 26 083- abroad

ff -CZ ²

wherein

m is the numbers 0, 1, 2 or 3,

Q ¹ and Q ^{2 are} each for oxygen or sulfur ι

Z ^{1 is} in each case optionally halogen,

Cyano, nitro, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, dialkylamino, carboxy and / or alkoxycarbonyl

substituted phenyl or naphthyl, or for 20

an optionally substituted by halogen and / or alkyl heterocyclic moiety from the series furyl, tetrahydrofuryl, oxotetrahydrofuryl, thionyl, tetrahydrothial

nyl, perhydropyranyl, oxazolyl, thiazolyl,

Thiadiazolyl, dioxolanyl, perhydropyrrolyl, oxoperhydropyrrolyl, pyridinyl or pyrimidinyl,

Z * for hydrogen, for optionally by halogen

halogen, alkoxy or alkoxycarbonyl-substituted alkyl, optionally substituted by halogen and / or alkyl cycloalkyl, alkenyl, benzyl or optionally

Halogen, cyano, nitro, alkyl, haloalkyl, 35

Le A 26 083 "abroad

Alkoxy "haloalkoxy" alkylthio "haloalkylthio and / or alkoxycarbonyl substituted phenyl" for alkoxy "benzyloxy" phenoxy "alkylthio" benzylthio "phenylthio or oialkylamino, and

Z and Z are each optionally substituted by halogen substituted alkyl or alkoxy «

in addition to diluents and / or surface-active substances included «provided *

According to the invention, the novel halogen-substituted phenoxybenzyl (thi) ol-derivatives of the general formula (I) are obtained when

(a) Halogen-substituted phenoxybenzyl halides of the general formula (II)

in which

R, R, R, R «R and X are the abovementioned Be

have meanings and

X ¹ stands for halogen.

with nucleophilic compounds of the general formula (III)

M-Y-Z (III) 5

in which

Y and Z have the meanings given above

and 10

M stands for hydrogen, sodium or potassium «

if appropriate in the presence of acid acceptors and, if appropriate, in the presence of diluents, or if

(b) halogen-substituted phenoxybenzyl (thi) ols of the general formula (Ia)

F ² R ¹ CH ₂ -YH

R3 <V (K Vx (Ia) R ⁴ R ⁵

in which

R ¹ IR ² , R ³ , R ⁴ i R ⁵ , X and Y are those indicated above Have meanings

with electrophilic compounds of the general formula (IV)

X ² - Z (IV)

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in which 5

Z is as defined above hai and X ^{2 is} a nucleophilic leaving group ι

if appropriate in the presence of acid acceptors and, if appropriate, in the presence of diluents, or if

(c) Halogen-substituted phenoxybenzylthiol derivatives of the general formula (Ib)

R ² R ¹ CH ₂ -SZ

in which

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , X and Z have the above ² "meanings"

with oxidizing agents »if appropriate in the presence of diluents»

Finally, it was found that the new halogen-substituted phenoxybenzyl (thi) ol derivatives of the formula (I) have outstanding herbicidal properties.

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Surprisingly, the halogen-substituted phenoxybenzyl (thi) ol derivatives of the formula (I) according to the invention are significantly more effective against weeds than methyl 3- (2,4-dichlorophenoxy) -6-nitrobenzoate, which is a structurally similar prior art active ingredient

same direction of action is · 10

The invention preferably relates to compounds of the formula (I) »in which

R ^{1 is} hydrogen »fluorine, chlorine» bromine »cyano or trifluoromethyl,

R ^{2 is} hydrogen, fluorine, chlorine or bromine,

R ³ represents fluorine, chlorine, bromine, cyano, trifluoromethyl, trifluoromethoxy or ^Λ trifluoromethylsulfonyl,

R ^{4 is} hydrogen, fluorine, chlorine or bromine, R ^{5 is} hydrogen, fluorine, chlorine or bromine

with the proviso that at least two of the substituents R ¹ , R ² , R ⁴ and R ⁵ are different from hydrogen,

30

35

X is fluorine, chlorine or bromine,

Y is oxygen, sulfur, sulfinyl or sulfonyl and

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fc - "" ^

Z is hydrogen, optionally substituted by cyano, fluorine "chlorine, bromine, hydroxy" C ₁ -C 4 -alkoxy, C ₁ -C 4 -alkylthio "carboxy" C ₁ -C 4 -alkoxycarbonyl "C ₁ -C 4 -alkyl- Alkyl-carbonyloxy or Cj-C ^ -alkoxycarbonyl-Cj-C ^ alkoxycarbonyl Cj-C ^ -C ^ alkyl substituted »depending Weil optionally by fluorine» chlorine »bromine and / or C ₁ -C ₄ -A ^ yI substituted Cg-Cg-cycloalkyl or _{C3-C8-cycloalkyl-Cj-C 4} alkyl "is optionally substituted by fluorine, respectively" chlorine and / or bromine, Cg-C ₆ alkenyl or C ^ Cg-alkynyl "or a the following definitions

Q ¹ Q ²

1 M 2

- <CH ₂ ) _m -zl, -CZ *,

wherein

m stands for the numbers 0 »1» 2 or 3 »

Q ¹ and Q ^{2 are} each oxygen or sulfur,

Z ^{1 is} in each case optionally substituted by fluorine "chlorine" bromine "iodine, cyano" nitro, C ₁ -C ₄ alkyl, fluoro

substituted and / or chlorine-substituted C ₁ -C ₂ -alkyl, C ₁ -C ₄ -alkoxy, fluorine-substituted

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and / or chloro-substituted C ₁ -C ₂ -alkoxy, C ₁ -C ₄ -alkylthio, fluoro-substituted and / or chlorine-substituted C ₁ -C -alkylthio, di- (C ₁ -C ₂ -alkyl) -amino, carboxy and / or C ₁ -C ₄ -alkoxy-carbonyl "ubstituiertes phenyl or naphthyl" or an optionally substituted by fluorine, chlorine, bromine and / or C ₁ -C ₄ -A ^ yI substituted heterocyclic moiety of "the series furyl» tetrahydrofuryl "oxotetrahydro f uryl, Thienyl, tetrahydrothienyl ♦ perhydropyranyl, oxazolyl, thiazolyl, »thiadiazolyl , dioxolanyl, perhydropyrrolyl,» oxoperhydropyrrolyl, pyridinyl or pyrimidinyl,

Z ^{2 is} hydrogen, for optionally by Fluorine, chlorine, bromine, C ₁ -C ₄ -alkoxy or C ₁ -C ₄ -

·

Alkoxycarbonyl-substituted C ₁ -C 12 -alkyl,

is optionally substituted by fluorine, chlorine, bromine and / or C | _-C4 ~ alkyl substituted Cg-C ^ - cycloalkyl, C ₃ -C ₆ -AIkOnW, benzyl or optionally substituted by fluorine, chlorine, bromine, iodine,

Cyano, N.Uro, Ci-C-alkyl, fluorine-substituted

and / or chlorine-substituted C ₁ -C ₂ -alkyl _# C ₁ -C ₄ alkoxy, fluorsubstituiertee and / or: hlorsubetituiertes C ₁ -C 2 -alkoxy, Cj-C ₄ alkylthio, fluorine-substituted and / or C ₁ -C ₂ chlorsubstituiertee -Alkylthio and / or C ₁ -C ₄ -alkoxy-CBr-

carbonyl-substituted phenyl, C ₁ -C ₄ -alkoxy, benzyloxy-phenoxy, C ₁ -C ₄ -alkylthio, benzylthio, phenylthio or di

stont, and 35

Le a 26 083 . foreign countries Z ³ and Z ^{4 are} each optionally fluorine

and / or chlorine-substituted C 1 -C ₄ -alkyl or C 1 -C ₄ -alkoxy are

The invention relates in particular to compounds of the

Formula (I) »in which 10

R ^{1 is} chlorine, R ^{2 is} hydrogen, R ^{3 is} trifluoromethyl, R ⁴ for hydrogen, fluorine or chlorine »

R ^{5 is} fluorine or chlorine, 20

X is chlorine or bromine, Y is oxygen, sulfur, sulfinyl or sulfonyl

stands and 25

Z FÜV hydrogen, represents optionally cyano-, fluorine, chlorine, hydroxy, Cj-C ₄ -alkoxy, Cj-C ₄ alkylthio, carboxy, Cj-C ^ alkoxy-carbonyl, Cj-C ₄ alkylcarbonyloxy or Cj-C _4- alkoxy-r.carbonyl-C ₁ -C 2 -alkoxycarbonyl-substituted C ₁ -C ₄ -alkyl) CyIf for any C ₃ -C 12 -cycloalkyl or C 9 -C 12 -cycloalkyl which is optionally hydrogenated by chlorine and / or methyl C ₁ -C ₂ -alkyl, in each case optionally substituted by chlorine C ₃ -C ₄ alkenyl or C ₃ -C ₄ -alkyl

kinyl, or stands for one of the following groups

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^ 2

c-z *

wherein

10

m stands for the numbers 0, 1 or 2 ι

Q ¹ and Q ^{2 are} each oxygen or sulfur »

15

Z ^{1 is} in each case optionally substituted by fluorine, chlorine,

Bromine, cyano, nitro, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, difluoro-

methylthio, trifluoromethylthio, dimethylamino 20

and / or methoxycarbonyl-substituted phenyl or naphthyl, or represents an optionally substituted by chlorine and / or methyl heterocyclic moiety from the series furyl, tetrahydrofuryl, thienyl, perhydropyranyl, oxazolyl, thiazolyl or dioxolanyl,

Z ^{2 is} hydrogen, for optionally by

Fluorine, chlorine, C ₁ -C ₂ -alkoxy or C ₁ -C ₂ -alkoxycarbonyl-substituted C ₁ -C ₄ -alkyl; for optionally chlorine and / or methyl-substituted C ₃ -C -cycloalkyl, C ₃ -C 4 -alkenyl , Benzyl, optionally substituted by fluorine, chlorine,

35

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Bromine »nitro» methyl »ethyl» tri fluorine thy 1 »methoxy» ethoxy »difluoromethoxy» trifluoromethoxy and / or methoxycarbonyl substituted phenyl or represents dimethylamines »and

Z ³ and Z ^{4 are} each C ₁ -C ₃ -alkoxy.

Examples of the compounds of the formula (I) according to the invention are listed in Table I below - see also the preparation examples,

Table It Examples of the compounds of the formula (I)

R ² R ¹

R ⁴ R ⁵

CHO-Y-Z

(I)

R ¹ R Cl H Cl H Cl H Cl H Cl H Cl H Cl H

CF,

CF,

CF,

CF,

CF,

CF,

CF,

H Cl Cl O H H Cl Cl S H H F Cl O H H F Cl S H Cl Cl Cl O H Cl Cl Cl S H F Cl Cl O H

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- 13 -

Table 1 - continued

γ ζ

Cl H CF ₃ F Cl Cl S H Cl H CFG H Cl br 0 H Cl H CFG H Cl Br I S H Cl H CFG H F br 0 H Cl H CF ₃ H F br S H Cl H CF ₃ Cl Cl br 0 H Cl H CFG Cl Cl br S H Cl H CF ₃ F Cl br 0 H Cl H CF ₃ F Cl br S H Cl H CF ₃ H Cl Cl 0 CH ₃ Cl H CF ₃ H Cl Cl S CH ₃ Cl H CF ₃ H Cl Cl 0 CHF ₂ Cl H CF ₃ H Cl Cl S CHF ₂ Cl H CF ₃ H Cl Cl 0 CF ₂ CHFCl Cl H CF ₃ H Cl C! S CF ₂ CHFCl Cl H CF ₃ H Cl Cl 0 C ₂ H ₅ Cl H CF ₃ H Cl Cl S C ₂ H ₅ Cl H CF ₃ H Cl Cl 0 C ₃ H ₇ Cl H CF ₃ H Cl Cl S C ₃ H ₇ Cl H CF ₃ H Cl Cl 0 CH (CHg) ₂

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- 14 -

Table 1 - continued

R ¹ R ² R ³ R ⁴ R ⁵ X Y Z Cl H CF ₃ H Cl Cl S CH (CHg) ₂ Cl H CF ₃ H Cl Cl 0 C ₄ H ₉ Cl H CF ₃ H Cl Cl S CH ₂ CHiCH ₃ ) ₂ Cl H CF ₃ H Cl 'Cl 0 CH ₂ CH ₂ OH Cl H CF ₃ H Cl Cl S CH ₂ CH ₂ OH Cl H CF ₃ H Cl Cl 0 CH ₂ CH ₂ CN Cl H CF ₃ H Cl Cl S CH ₂ CH ₂ CN Cl H CF ₃ H Cl Cl 0 CH ₂ CN Cl H CF ₃ H Cl Cl S CH ₂ CN Cl H CF ₃ H Cl Cl 0 CH ₂ CH ₂ OCHg Cl H CF ₃ H Cl Cl S CHgCHgOCHg Cl H CF ₃ H Cl Cl 0 CH ₂ CH ₂ SCH ₃ Cl H CF ₃ H Cl Cl S CHgCHgSCHg Cl H CF ₃ H Cl Cl 0 CH ₂ COOH Cl H CF ₃ H Cl Cl S CH ₂ COOH Cl H CF ₃ H Cl Cl 0 CH ₂ COOCH ₃ Cl H CF ₃ H Cl Cl S CH ₂ COOCH ₃ Cl H CF ₃ H Cl Cl 0 CH ₂ COOC ₂ H ₅ Cl H CF ₃ H Cl Cl S CH ₂ COOC ₂ H ₅ Cl H CF ₃ H Cl Cl 0 CH ₂ COOCH ₂ COOCHg

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Table 1 - continued

R ¹ R ² R ³

R ⁴ R ⁵ X YZ

Cl H CF ₃ H Cl Cl S Cl H CF ₃ H Cl Cl 0 Cl H CF ₃ H Cl Oil S Cl H CFo H Cl Cl O

CH ₂ COOCH ₂ COOCh ₃ CH ₂ COOCHCOOCh ₃

CH ₃ CH ₂ COOCHCOOCh ₃

CH ₃ CHCOOCHo

I ³

CH ₃

Cl H CF ₃ H Cl

Cl S CHCOOCH-:

Cl H CF ₃ H Cl Cl O 20

Cl H CF ₃ H Cl Cl S Cl H CF ₃ H Cl Cl 0

CH ₃

CHCOOC ₂ H ₅

CH ₃

CHCOOC ₂ H ₅

CH ₃

/ CH ₂ -CH I

/ CH ₂ HI

Cl H CF ₃ H Cl Cl S -CH | Cl H CFo H Cl Cl 0 Cl H CFo H Cl Cl S Le A 26 083 »Aueland

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Table 1 - continued

R ¹ R ² R ³ R ⁴ R ⁵ X YZ

Cl H CFq H Cl Cl Cl H CF ₃ H Cl, Cl S Cl H CFo H Cl Cl Cl H CFq H Cl Cl S Cl H CFq H Cl Cl S CH ₉ -CH Cl H CF ₃ H Cl Cl

/ CH ₂

CH '

Cl H

Cl Cl

Cl H CFG H Cl Cl 0 CH ₂ CH = CH ₂ Cl H CF ₃ H Cl Cl 0 CH ₂ CH = CHCH ₃ Cl H CF ₃ H Cl Cl S CH ₂ CH = CH ₂ Cl H CF ₃ H Cl Cl 0 CH ₂ CSCH Cl H CF ₃ H Cl Cl S CH ₂ CSCH

Cl H

Cl Cl

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- 17 -

Table 1 - continued

R ¹ R ² R ³

R ⁴ R ⁵ X YZ

Cl H CFo H Cl Cl S CH ' Cl H CFo H Cl Cl S Cl H CF ₃ H Cl Cl S CH ₂ Cl H CFo H Cl Cl O Cl H CFo H Cl Cl S Cl H CFq H Cl Cl O Cl H CFq H Cl Cl O Cl H CFq H Cl Cl O

Cl

Cl H CF ₃ H Cl Cl O Cl H CFq H Cl Cl O Le A 26 083 - Foreign countries

- 18 -

T able 1 - continued

R ^ö X YZ

3757

Cl H CFq H Cl Cl 0 Cl H CFq H Cl 'Cl 0

N (CHg) ₂

00CH ₃

Cl H

H Cl Cl O

Cl H CFq H Cl Cl O

Cl H CF ₃ H Cl Cl O Ch ₂

Cl H CFq H Cl Cl O

Cl H

Cl Cl

H CF ₃ H Cl Cl 0 CH ₂ ^^ O ^ Cl H CF ₃ H Cl Cl O CO Chg Cl H CF ₃ H Cl Cl O CO-C ₂ H ₅ Cl H CF ₃ H Cl Cl O CO-C ₃ H ₇ Cl H CF ₃ H Cl Cl O CO-CH (CHg) ₂ Cl H CF ₃ H Cl Cl O CO-C ₄ H ₉ Cl H CF ₃ H Cl Cl O CFG Cl CO-CH ₂ Cl

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- 19 -

Table 1 - continued

10

20

rl r2 r3 R ⁴ R ⁵ X Y Z Cl H CF ₃ H Cl Cl O Cl H CF ₃ H Cl Cl O CO-CHCl ₂ Cl H CF ₃ H Cl Cl O CO-CCl ₃ Cl H CFG H Cl Cl O CO-CH ₂ CH ₂ Cl Cl H CFG H Cl Cl O CO-CH ₂ OCH ₃ Cl H CF ₃ H Cl Cl O CO-CH ₂ COOCH ₃ Cl H CF ₃ H Cl Cl O CO-CH ₂ COOC ₂ H ₅ / CH ₂ CO-CH I Cl H H CF ₃ CFg H H Cl Cl Cl Cl O O ^ CH ₂ Cl CO /

25

Cl H CFo H Cl Cl 0 C0 ~ H Cl H CFo H Cl Cl 0 CO-CH = CHCHr Cl H CFo H Cl Cl 0 Cl) -CH-

30

Cl H CFo H Cl Cl O C Cl H CFo H Cl Cl O C Le A 26 083 · Aueland

- 20 -

Tahelle 1 - continued

R ¹ R ² R ³ R ⁴ R ⁵ X YZ

Cl H CFq H Cl Cl 0 C Cl H CF-Λ H Cl Cl 0 C Cl H CFq H Cl Cl 0 C Cl H CFq H Cl Cl 0 C Cl H CF ₃ H Cl Cl 0 C Cl H CFo H Cl Cl 0 C Cl H CFq H Cl Cl 0 C

00CH ₃

Cl H CF ₃ H Cl Cl 0 P (OCHg) ₂

Il Cl H CF ₃ H Cl Cl 0 P (OC ₂ Hg) ₂

Cl H CFq H Cl Cl S

Il P (OCHg) ₂

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- 21 -

Table 1 - continued

R ⁴ R ⁵ X

Cl

Cl

CF;

Cl

Cl

I!

Cl SP (OC ₂ Hg) ₂

• Cl 0 P (OC ₂ Hg) ₂

Cl H CF ₃ H Cl Cl S P (OC ₂ Hg) ₂ Cl H CFG H F Cl 0 CH ₂ COOCH ₃ Cl H CF ₃ H F Cl S CH ₂ COOCH ₃ Cl H CF ₃ H F Cl 0 CH ₂ COOC ₂ H ₅ Cl H CF ₃ H F Cl S CH ₂ COOC ₂ H ₅ Cl H CF ₃ H F Cl S CH ₂ COOCh ₂ COOCH ₃ Cl H CF ₃ H F Cl S CH ₂ COOCH ₂ COOc ₂ H ₅ Cl H CF ₃ H F Cl S CH ₂ COOCHCOOCh ₃ CH ₃ Cl H CF ₃ H F Cl S CH ₂ C00CHC00C _s H ₅ CH ₃ Cl H CF ₃ H F Cl 0 CO-CH ₂ COOCH ₃ Cl H CF ₃ H F Cl 0 CO-CH ₂ COOC ₂ H ₅

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10

If, for the process (a) 2-fluoro-5- (2,6-difluoro-4-trifluoromethyl-phenoxy) benzyl bromide and 2-ethylthio-et'nanoi they are starting materials, the reaction sequence by the following formula Scheme be reproduced:

- HBr

CH ₂ -Br

HO-CH ₂ CH ₂ -SC ₂ H ₅

CH ₂ -O-CH ₂ CH ₂ -SC ₂ H ₅

20 25 30; J5

If, for the process (b) according to the invention, 2-bromo-5- (2-chloro-5,6-difluoro-4-trifluoromethyl-phenoxy) -benzylthiol and chloroacetitrile are used as starting materials, the course of the reaction can be represented by the following equation:

Cl

F F

HCl

Cl-CH ₂ -CN

CH ₂ -S-CH ₂ -CN

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If, for the process (c) according to the invention, 5- (2-chloro-5- (2,6-dichloro-4-trifluoromethyl-phenoxy) -benzyl) -mercRptoeBsigsäure-methyl ester and hydrogen peroxide as starting materials, the reaction sequence by the following formula scheme be reproduced:

Cl CHo-S-CH ₂ COOCHo

H ₉ O

CH ₂ -SO-CH ₂ COOCH 15

The halogen-substituted phenoxybenzyl halides to be used as starting materials in process (a) according to the invention for the preparation of compounds of the formula (I) are generally defined by the formula (II).

In formula (II), R ^1, R ^2, R ^3, R ^4, R ⁵ and X respectively Preferably, "in particular have those meanings" already mentioned above in connection with the description of erfindungegemäßen compounds of formula (I) preferably or "as insbesondera preferably R ¹ , R ² > R ³ , R ⁴ _} R ⁵ and X have been indicated and X ⁷ · is preferably chlorine or bromine.

Examples of the starting materials of the formula (II) are listed in Table 2 below.

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Table 2i Examples of the starting materials of the formula ⁵ (II)

10

(II)

15 20 25 30 35

Cl H CF ₃ H Cl Cl Cl Cl H CF ₃ H Cl br Cl Cl H CF ₃ H egg Cl br Cl H CF ₃ H Cl br br Cl H CF ₃ H F Cl Cl Cl H CF ₃ H F br Cl Cl H CF ₃ H F Cl br Cl H CF ₃ H F br br Cl H CFG F Cl Cl Cl Cl H CF ₃ F Cl br Cl Cl H CF ₃ F Cl Cl br Cl H CF ₃ F Cl br br Cl H CF ₃ Cl Cl Cl Cl Cl H CF ₃ Cl Cl br Cl Cl H CFG Cl Cl Cl br Cl H CFG Cl Cl br br Cl H CF ₃ F F Cl Cl

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The starting materials of the formula (II) are known (cf., EP-A 23 890 »EP-A 56 119) or subject of a non-prepublished patent application [P 38 12 768.7 of 16.4.1988 (Le A 25 995)].

The starting compounds of the formula (II) are obtained when appropriate halogen-substituted phenoxytoluene derivatives of the general formula (V)

(V) 15

in which

R ¹ IR ² , R ³ i R ⁴ # R ⁵ and X have the meanings given above »

with halogenating agents »such. Chlorine, bromine, sulfuryl chloride, N-chloro- or N-bromo-buccinimide, optionally under exposure, for example with mercury.

immersion lamps "if appropriate in the presence of catalysts" such as "benzoyl peroxide or azo-bis-isobutyronitrile" and, if appropriate, in the presence of diluents, such as ζ. Β «Tetrachloromethane» b'ji temperatures between 20 ⁰ C and 150 ⁰ C converts.

The halogen-substituted phenoxytoluene Deriyate of formula (V) are known and / or can be prepared by processes known per se (see, DE-AS 23 04 006),

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- 26 -

The nucleophilic compounds to be used further as starting materials in process (a) according to the invention are generally defined by the formula (III).

In formula (III), Y and Z preferably or in particular have those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention preferably or rather preferably as Y and Z, and M is preferably Hydrogen or sodium «

As examples of the starting materials of the formula (III) may be mentioned S

Water »Hydrogen Sulphide» Methanol »Ethanol» Propanol »Isopropanol» Butanol »Isobutanol» sec-Butanol »tert-Butanol» Methanethiol »Ethanethiol» Propanethiol »1-Methylethanethiol» Butanethiol »2-Methylbutanethiol, and 1» 1-Dimethyl -ethanethiol »ethylene glycol» propylene glycol, 2-methoxy- and 2-ethoxy-ethanol »2-methylthio- and 2-ethylthio-ethanol» glycolic acid and lactic acid and their methyl esters and ethyl esters »cyclopropyl, cyclobutyl» cyclopentyl and cyclohexyl alcohol »cyclopropyl - »Cyclobutyl-» cyclopentyl- and cyclohexylmethanol »allyl alcohol» crotyl alcohol »propargyl alcohol» benzyl alcohol »phenol» 2-fluoro-, 4-fluoro- »2-chloro-» 3-chloro- »4-chloro-» 3,4-dichloro - »4-bromo, 4-iodo, 2-methyl-» 3-methyl-, 4-methyl-, 3 »4-dimethyl-, 2-methoxy-, 3-methoxy-» 4-methoxy- »3 , 4-dimethoxy, 3-dimethylamino, 4-dimethylamino, 2-methoxycarbonyl, 3-methoxycarbonyl, 4-methoxycarbonyl, 3-trifluoromethoxy, and 4-trifluoro-

methoxy-phenol »1-naphthol» 2-naphthol »2-hydroxymethyl-35

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furan »2-hydroxymethyltetrahydrofuran, 2-hydroxymethylperhydropyran and 4-hydroxymethyl-l, 3-dioxolan«

The starting materials of the formula (III) are known organic synthesis chemicals.

The novel process (a) for the preparation of the novel compounds of the formula (I) is preferably carried out using diluents. Suitable diluents are virtually all inert organic solvents. These include, preferably, aliphatic and aromatic halogenated or unsubstituted hydrocarbons, such as pentane or hexane »Heptane» Cyclohexane »Petroleum ether» Gasoline »Ligroin» Benzene »Toluene, xylene, methylene chloride» Ethylene chloride »Chloroform» Carbon tetrachloride »Chlorobenzene and o-dichlorobenzene» Ethers such as diethyl and dibutyl ether »Glycol dimethyl ether and diglycol dimethyl ether» Tetrahydrofuran and dioxane »Ketones such as acetone» Methyl ethyl, methyl isopropyl and methyl isobutyl ketone, esters such as methyl acetate and ethyl acetate, nitriles such as acetonitrile and propionitrile, amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and dimethyl sulfoxide »Tetramethylene sulfone and hex amethylphosphorsäuretriamid "

Suitable acid acceptors in the process (a) according to the invention are all acid binders customarily used for such reactions. Preference is given to alkali metal hydroxides, such as

z. B, sodium and potassium hydroxide »Earth1kai! Hydroxide 35

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as ζ »Β« calcium hydroxide »alkali carbonates, hydrides and alcoholates such as sodium and potassium carbonate» sodium and potassium hydride »sodium and potassium tert-butoxide» further aliphatic »aromatic or heterocyclic amines» for example triethylamine »trimethylamine» dimethylaniline »Dimethylbenzylamine» Pyridine »1» 5-diazabicyclo- [4,3,0] -non-5-ene (DBN), 1 »8-diazabicyclo [5,4» 0] undec-7-βη (DBU) and 1 "4-diazabicyclo-C2" 2 "-octane (DABCO),

The reaction temperatures in the process (a) is varied within a substantial range "In general, the reaction is preferably carried out at temperatures between ⁰ C and 150 ⁰ C ₁ at temperatures between 10 ⁰ C and 100 ⁰ C.

The process (a) according to the invention is generally carried out under atmospheric pressure.

In order to carry out process (a) according to the invention, the particular starting materials required are generally employed in approximately equimolar amounts. However, it is also possible to use one of the two components used in each case in a larger excess. The reactions are generally carried out in a suitable diluent in The presence of an acid acceptor is carried out »and the reaction mixture is stirred for several hours at the temperature required in each case« The work-up is carried out in the inventive method (a) in each case by conventional methods «

Le A 26 083 - Foreign countries

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The in process (b) for the preparation of compounds of formula (I) as starting materials to be used halogen-substituted PhenoxybenzyKthi) ole are generally defined by the formula (Ia) «

In formula (Ia), R ^1, R ^2, R ^3, R ^4, R ^5, X and Y preferably or "in particular have those meanings * which respectively (I) above in connection with the description of the compounds of the formula according to the invention preferably" as particularly preferred for R ¹ , R ² , R ³ ,

R ⁴ , R ^, X and Y were given »15

Examples of the starting materials of the formula (Ia) are shown in Table 1 (Z "H)",

The starting materials of the formula (Ia) are novel compounds according to the invention; they can be prepared by the process (a) according to the invention »

The in process (b) according to the invention as starting materials to be used electrophilic compounds are generally defined by the formula (IV).

In formula (IV) Z preferably or "in particular has that meaning" which has already been mentioned above in connection with the description of the compounds of the formula (I) preferably or "Z is particularly preferred and X ² is preferably chlorine" bromine * Iodine optionally substituted by fluorine or chlorine-substituted Cj-C ^ alkylsulfonyloxy or optionally substituted by fluorine, chlorine, bromine or methyl substituted

Le A 26 083 - Foreign countries

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Phenylsulfonyloxy, in particular chlorine, bromine, methylsulfonyloxy, phenylsulfonyloxy or 4-methylphenylsulfonyloxy,

As examples of the starting materials of the formula (IV) may be mentioned:

* 0 Methyl- »ethyl-» propyl- »isopropyl-» butyl- »isobutyl-, sec-butyl- and tert-butylchloride» bromide and iodide »chlorodifluoromethane» 1 »2-dichloro-1» 1 , 2,2-tetrafluoroethane »allyl chloride» benzyl chloride »2-fluoro, 4-fluoro-2-chloro-3-chloro, 4-chloro-2,6-dichloro, 4-methyl-, 4-

** Methoxy- and 4-methoxycarbonyl-benzyl chloride »acetyl chloride» propionic acid chloride, buty acid chloride, isobutyric acid chloride »valeric acid chloride» isovaleric acid chloride »chloroacetyl chloride» dichloroacetyl chloride »trichloroacetyl chloride» 2-chloro-propionic acid chloride »

^ ⁰ Methoxyacetyl chloride »cyclopropane» cyclobutane cyclopentane and cyclohexane-carboxylic acid chloride »crotonic acid chloride» phenylacetic acid chloride »benzoyl chloride» 2-fluoro, 4-fluoro »2-chloro, 3-chloro, 4-chloro» 3,4- Dichloro-, 2-nitro-, 4-nitro- »4-methyl-, 4-methoxy- and 4-methoxycarbonyl-benzoyl chloride» dimethylchlorophosphate »diethylester» dipropylester »diisopropylester and -dibutylester and thiophosphoric acid chloride-dimethylester» - Diethyl »-dipropylester» -diieopropylester and -dibutylester »Chloroacetonitrile»

3Q bromoacetonitrile, 0-bromo-propionitrile, beta-chloro-propionitrile, '- chloro, alpha-bromo, and' -iodo-propionic acid methyl ester, ethyl ester »propyl ester» isopropyl ester »butyl ester» isobutyl ester and sec butyl ester »0-chloro,

methyl β-bromo and β-iodo-propionate »ethyl ester» 35

Le A 26 083 - AüSJflnri

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-propyleater, -iaopropyleater "-butyleater" -ieobutyleater and -aec-butyleater, chloro-bromo and iodo-easegaic acid methyl ester «ethyl ester« propyl ester, -iaopropyleater «butyl-terephthalate» a-butylbutyl ester «a -Methylaulfonyloxy- "" -Ethylaulfonyloxy- "a-Propylsulfonyloxy-" "-Butylaul- fonyloxy-" "-Trifluoro-ethylaul- fonyloxy-" "-Phenylaul- fonyloxy-" and - (4-methyl-phenylsulfonyloxy) -propionic-methyleeter, ethyl-ester, -propylester, butyl ester, isopropyl ester, α-butylbutyl ester and sec-butyl ester,

The starting materials of the formula (IV) are known and / or can be prepared by processes known to aich (see, DE-OS 27 58 002 »DE-OS 28 54 542).

The process (b) according to the invention is preferably carried out in the presence of diluents. "Above all those organic solvents are considered" which were prepared above for process (a) as diluents. "

The process according to the invention (b) is optionally carried out in the presence of acid acceptor. The acid binders which have already been mentioned above for process (a) are particularly suitable.

The Reaktionatemperaturen can be varied in the process (b) according to the invention in a wider range "In general, it is preferably carried out at temperatures between ^{0 0} C and 150 ° C" at temperatures

between 20 ⁰ C and 100 ⁰ C.

 35

Le A 26 083 - Aueland

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Process (b) is generally carried out at atmospheric pressure.

In order to carry out process (b) according to the invention, the starting materials required are generally employed in approximately equimolar amounts. However, it is also possible to use one of the two components in a larger excess. The reactions are generally carried out in a suitable diluent in The presence of an acid acceptor is carried out «and the reaction mixture is stirred for several hours at the respective required temperature« The work-up is carried out in the inventive method (b) each by conventional methods «

The erfindxmgsgemäßen method (c) for the preparation of compounds of formula (I) as starting materials to be used halogen-substituted Phenoxybenzylthiol derivatives are generally defined by the formula (Ib).

In formula (Ib), R ^1, R ^2, R ^3, R ^4, R ^5, X and Z preferably or "in particular have those meanings," the already above in connection with the description of the compounds of the formula (I) "is preferably or Particularly preferred for R ¹ . R ² »R ³ , R ⁴ , R ⁵ , X and Z were given«

Examples of the starting materials of the formula (Ib) can be found in Table 1 (Y = S). «

Le A 26 083 - Foreign countries

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The starting materials of the formula (Ib) are novel compounds according to the invention; they can be prepared by the processes (a) and (b) according to the invention

The inventive process (c) is carried out using an oxidizing agent "It can SuIfoxiden din conventionally used for the oxidation of sulfides or SuIfönen useful oxidants are used" These include, for example, hydrogen peroxide "performic acid, peracetic acid, perbenzoic acid and 3-chloro-

perbenzoic acid «15

The inventive method (c) is preferably carried out using diluents. "These include organic solvents such as methylene chloride, chloroform, formic acid" acetic acid and

Propionic acid "also water"

The reaction temperatures can be varied in the process (c) according to the invention in a wider range. "In general, one works at temperatures between -30 ⁰ C and + 100 ⁰ C, preferably at temperatures between -10 ⁰ C and + 80 ⁰ C.

Process (c) is generally carried out under normal pressure.

To carry out the process (c) according to the invention, use is made of 1 mol of a halogen-substituted phenoxybenzylthiol derivative of the formula (Ib) in general

ie a 26 083 .Aueland

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0i9 to 1.5 molar equivalents, preferably 1.0 to 1.2 equivalents of an oxidizing agent (for the preparation of sulfoxides) or "1 * 9 to 2.8 molar equivalents, preferably 2.0 to 2.5 equivalents of an oxidizing agent (for the preparation of Sulfones) «

The reaction components are generally combined at room temperature or under KUhlon and the reaction mixture is stirred at the particular temperature required until the end of the reaction. The work-up in the process (c) according to the invention is carried out in each case by customary methods.

The active compounds according to the invention can be used as defoliants, desiccants, herbicide and, in particular, as weedkillers. "Weeds in the broadest sense are understood to mean all plants which grow up in places where they are undesirable." Whether the substances according to the invention act as total or selective herbicides depends essentially from the quantity applied «25

The active compounds according to the invention can be used «B« in the following plants:

Dikotvle weeds of the genera. ' Sinapis, Lepidium, Ga * "liurn" Stellaria, Matricaria, Anthemis, Calinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, ragweed, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Labium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsit! »Papaver, Centaurea«

Le a 26 083. foreign countries

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pikotyle cultures of the genera " Gossypium, Glycine, Beta" Daucus, Phaseolus, Pisumι Solanum, Linum, Ipomoea, Vicia, Nicotianai Lycopersicon, Arachis, Brassica, Lactucai Cucumis, Cucurbita "

Monocotyledonous weeds of the genera} Echinochloa, Setaria, Panicum »Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromusi Avena, Cyperus» Sorghum, Agropyron, Cynodon, Monochoria, Fimbrietylia _# Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum « spheno

clea »Dactyloctenium, Agrostis, Alopecurus» Apera «15

Monocot cultures of the genera? Orysa * Zea, Triticum, Hordeum, Avena, Seeale, Sorghum, Panicum, Saccharum, Pineapple, Asparagus, Allium «

However, the use of the active compounds according to the invention is by no means restricted to these genera, but extends in a similar manner to other plants. "

The compounds are useful depending on the concentration for total weed control e.g. on industrial and railway tracks and on paths and squares with and without tree cover. "Likewise, the weed control compounds may be used in permanent crops, e.g. Forestry, Ziehholz-, fruit, wine, citrus, Nu & -, banana, coffee, tea, gum, oil palm, cocoa, berry fruit and hop plants and used for selective weed control in annual crops.

35

Le A 26 083 . foreign countries

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The active compounds according to the invention are particularly suitable for the selective control of dicotyledonous weeds in monocotyledonous crops "especially in the post-emergence process"

Some of the compounds of the formula (I) according to the invention also have a fungicidal action "for example against Pyricularia oryzae on rice"

The active ingredients can be converted into the usual formulations »as solutions« Emulsions »Injection powders» Suspensions »Powders» Dusts »Pastes» soluble powders »Granules» Suspension emulsion concentrates »Active substance-impregnated natural and synthetic substances as well as ultra-fine encapsulations in polymeric substances«

These formulations are prepared in a known manner by mixing the active compounds with extenders, ie liquid solvents and / or solid carriers, if appropriate using surface-active agents, ie emulsifiers and / or dispersants and / or foam-forming agents.

In the case of using water as an extender, e.g. also organic solvents as auxiliary solvents

be used medium »As liquid solvents are essentially in question! Aromatics »such as xylene» toluene »or alkylnaphthalenes» chlorinated aromatics and chlorinated aliphatic hydrocarbons »such as chlorobenzenes» chloroethylene or methylene chloride »aliphatic

Le a 26 083 - Aueland

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Hydrocarbons such as cyclohexane or paraffins »e.g. Petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol, and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents,

such as dimethylformamide and dimethyl sulfoxide, and water · 10

Suitable solid carriers are: z, B. Ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as fumed silica, alumina and silicates, as solid carriers for granules are suitable: e.g. Cracked and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic

Flours and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; suitable emulsifying and / or foaming agents are, for example, nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates; suitable dispersants are: e.g. Lignin-sulphite liquors and methylcellulose «

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations. Other additives can be mineral and vegetable oils »

Le A 26 083 - Foreign countries

2 3 3 7 5 7

- 38 -

Dyes such as inorganic pigments, e.g. Iron oxide "titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The formulations generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90 %,

The active compounds according to the invention, as such or in their formulations, can also be used for combating weeds in admixture with known herbicides, ready-to-use formulations or tank mixes being possible «

For the mixtures are known herbicides such as "B" 1-amino-6-ethylthio-3- (2,2-dimethylpropyl) -1, 3,5-triazine-2,4 (1H, 3H) -dione (AMETHYDIONE) or N- (2-benzthiazolyl) -Ν, Ν'-dimethyl-urea (METABENZTHIAZURON) for weed control in cereals; 4-Araino-3-methyl-6-phenyl-l »2,4

triazine-5 (4H) -one (METAMITRON) for weed control in sugar beet and 4-amino-6- (1,1-dimethylethyl) -3-methylthio-l, 2,4-triazine-5 (4H) -one (METRIBUZIN ) for weed control in soybeans, in question »2,4-dichlorophenoxyacetic acid (2,4-D) -j 4- (2,4-dichlorophenoxy) -butyric acid

(2,4-DB) j 2,4-dichlorophenoxypropionic acid (2,4-DP); 3-Isopropyl-2,1,3-benzothiadiazin-4-one-2,2-dioxide (BEN-TAZON); Methyl 5- (2,4-dichlorophenoxy) -2-nitrobenzoate

Le A 26 083 · abroad

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(Bifenox); 3,5-dibromo-4-hydroxybenzonitrile (BROMOXY-NIL); 2-chloro-N - {[4-methoxy-6-methyl-1, 3,5-triazin-2-yl) amino] carbonyl} benzene-8-sulfonamide (CHMDRSULFURON); N ₁ N-dimethyl-N '- (3-chloro-4-methylphenyl) -hardenoic (CHLO RTOURR); 2- [4- <2,4-dichlorophenoxy) -phenoxy-3-propionic acid * its methyl or its ethyleater (DICLO-FOP); 4-amino-6-t-butyl-3-ethylthio-1, 2,4-triazine-5 (4H) -one (ETHIOZIN); 2- {4 - [(6-chloro-2-benzoxazolyl) -oxy] -phenoxy} -propanoic acid, its methyl or ethyl acetate (FENOXAPROP); Methyl 2- [4,5-dihydro-4-methyl-4- (1-methylethyl) -5-oxo-1H-imidazol-2-yl] -4 (5) -methylbenzoate (IMAZAMETHABENZ); 3,5-diiodo-4-hydroxybenzonitrile (IOXY-NIL); N _# N-dimethyl-N '- (4-iaopropylphenyl) urea (ISOPROTURON); (2-methyl-4-chlorophenoxy) -acetic acid (MCPA); N-methyl-2- (1,3-benzthiazol-2-yloxy) -acetanilide (MEFENACET); 2 - {[[(4-methoxy-6-methyl-1, 3,5-triazin-2-yl) amino) carbonyl] amino] sulfonyl} benzoic acid or its methyl ester (METSULFURON); N- (1-ethyl-propyl) -3,4-dimethyl-2,6-dinitroaniline (PENDIMETHALIN); 0- (6-chloro-3-phenyl-pyridazin-4-yl) -S-octyl-thiocarbonate (PYRIDA-TE); 4-ethylamino-2-t-butylamino-6-methylthio-s-triazine (TERBUTRYNE); Methyl 3 - [[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl) amino] carbonyl] amino] sulfonyl] thiophene-2-carboxylate (THIAMETURON) and 3,5,6-trichloro-2-pyridyloxyacetic acid (TRICLOPYR). Some mixtures show

surprisingly also synergistic effect «30

Also a blend with other known active ingredients, such as fungicides «insecticides» acaricides, nematicides, bird repellants, plant nutrients and

Soil structure improvers are possible · 35

Le a 26 083. Aueland

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The active compounds can be used as such "in the form of their formulations or the use forms prepared therefrom by further dilution" such as ready-to-use solutions "suspensions" emulsions "powders" pastes and granules. by pouring »spraying» spraying »spreading«

The active ingredients according to the invention can be applied both before and after emergence of the plants. «

They can also be worked into the soil before sowing. "

The amount of active substance applied may vary within a broad range. It depends essentially on the type of effect desired. In general, the application rates are between 0.01 and 10 kg of active ingredient per hectare of soil surface, preferably between 0.5 and 5 kg per ha.

The preparation and use of the invention

Active ingredients are shown in the following examples,

Le A 26 083 . Aueland

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AusfQhrung8bei8piele

Herstellungebeispiele Cl V CH \ -COOC ₂ H ₅ example 1 .0. ₂ -S-CH ₂ _ci -Z ⁷

(Method (a))

A mixture of 2.88 g (0.024 mol) of ethyl mercaptoacetate »0.75 g of sodium hydride (80 % ± g in paraffin oil) and 150 ml of tetrahydrofuran is stirred for 15 minutes at 20 ^° C. Then a solution of 8 * 7 g (0 , 02 mol) of 2-chloro-5- (2,6-dichloro-4-trifluoromethyl-phenoxy) benzyl bromide in 50 ml of tetrahydrofuran are added dropwise with stirring and then the mixture is stirred at 60 ⁰ C for 2 hours. After concentration, the residue is taken up in methylene chloride / water and extracted by shaking. The organic phase is separated, dried with magnesium sulfate and filtered. From the filtrate, the solvent is carefully distilled off in a water-jet vacuum.

This gives 8.5 g (90 % of theory) of 2-chloro-5- (2,6-dichloro-4-trifluoromethyl-phenoxy) -benzylthio-e-hydroxyacetic acid ethyl ester as pale yellow DIv

¹ H-NMR _(CDCl3, S) x 1.15 (t, OCH ₂ CH ₃₎ I 4.05 (q, OCH ₂ CH _3);

Cl

8.15 (8, F ₃ C

- 42 -

Analogously to Example 1 and according to the general description of the preparation process according to the invention, the compounds of the formula (I) listed in Table 3 below can be prepared «

Table 3? Preparation examples of the compounds of the formula (I)

CH ₂ -YZ

Ex, -No.

Y Z

Melting point ( ⁰ C)

Cl H CFo H Cl Cl O CO-CHr Cl H CF ₃ H Cl Cl OC

(6 = 5.18) *

10

Cl H CF ₃ H Cl Cl

5 Cl H CF ₃ H 6 Cl H CF ₃ H 7 Cl H CF ₃ H 8th Cl H CF ₃ H 9 Cl H Cfo H

Cl Cl S H 123

Cl Cl S CH ₂ CH ₂ OH (6 = 3.70) * Cl Cl 0 CHCOOC ₂ H ₅ (6 = 4.19) *

CHO

Cl Cl 0 H Cl Cl 0 CH ₃

Cl H CFo H Cl Cl

COOCH ₃

116 64

110

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Table 3 - continued Nr, R ¹ R ² R ³ R ⁴ R ⁵ X YZ

Melting point ( ⁰ C)

11 Cl H CFo H Cl Cl O

12 Cl H CFo H Cl Cl O

124

COOCH ^

OOCHo

13 Cl H CFo H Cl Cl O

112

14 Cl H CFq H Cl Cl O

Cl

15 Cl H CFq H Cl Cl 0

78

1 84

16 Cl H CF ₃ H Cl Cl 0

OCH ":

108

17 Cl H CF ₃ H Cl Cl 0

OCH.

77

18 Cl H CF ₃ H Cl Cl 0 V-OCH ₃ (6 = 3.79) *

19 Cl H CF ₃ H Cl Cl S CH ₂ COOCH ₃ (6 = 3.79) *

20 Cl H CF ₃ H Cl Cl 0 CH (CH ₃ J ₂ (6 = 4.55) *

Le A 26 083 «Aueland

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Table 3 - continued Example, - melting No. R ¹ R ² R ³ R ⁴ R ⁵ X YZ point < ^C C)

21 Cl H CF ₃ H Cl Cl S CH ₂ COOH 114

22 Cl H CF ₃ H Cl Cl 0 CO-CH ₂ COOCH ₃ (5 = 5.25) *

23 Cl H CFo H Cl Cl S CHoCOOCHCOOCHo

³ , * | ? 6 = 3.70) *

CH ₃

24 Cl H CF ₃ H Cl Cl S CH ₂ CuOCH ₂ COOCH ₃ (6 = ^3.68):

25 Cl H CF ₃ Cl Cl Cl 0 COCHg 92 15

26 Cl H CFg Cl Cl Cl S CH ₂ COOCHg 50

27 Cl H CF ₃ H Cl Cl 0 CO-CH (CHg) ₂ 74

28 Cl H CFg Cl Cl Cl S CH ₂ COOC ₂ H ₅ (6 = 3.79) *

29 Cl H CF ₃ H Cl Cl S CN (CHO) ₅ . 110 ^y

S Cl Cl Cl S CH ₂ COOH (6 = 3.88) *

F Cl 0 COCH ₃ (6 = 5.17) *

F Cl S CH ₂ CH ₂ OH (6 = 3.80) *

F Cl 0 COCH (CHg) ₂ (6 = 5.17) * F Cl S CH ₂ COOCH ₃ 35

__ .. _. Cl Cl S CN (CqH ₇ -Do 70 ^J II

Cl Cl S CH ₂ CH ₂ OCOCH ₃ Cl Cl S CH ₂ CH ₂ OCOCH (CH ₃ ) ₂

38 Cl H CF ₃ HF Cl S CHCOOC ₄ H ₉

CH ₃

Lb a 26 083 - foreign countries

30 Cl H CF ₃ C 31 Cl H CF ₃ H 32 Cl H CF ₃ H 33 Cl H CF ₃ H 34 Cl H CF ₃ H 35 Cl H CF ₃ H 36 Cl H CF ₃ H 37 Cl H CF ₃ H 38 Cl H CF ₃ H

45 -

Table 3 - continued

Ρβρ, - No. R ¹ H R ³ R < RS χ Y Melting point ( ⁰ C) 39 Cl CF ₃ H F Cl S CHCOOC ₂ H ₅ H CH ₃ 40 Cl H CF ₃ H F Cl so CH ₂ COOCH ₃ 82 41 Cl H CF ₃ H F Cl S CH ₂ CH ₂ COOC ₂ H ₅ 42 Cl CF ₃ H Cl Cl S CHCOOC ₃ H ₇ CH ₃ H CH ₂ COOCH ₃ 43 Cl H CF ₃ H F Cl SO ₂ CHCOOC ₂ H ₅ 44 Cl CF ₃ H F Cl so CH ₃ H CH ₂ CH ₂ COOC ₂ H ₅ 45 Cl H CF ₃ H F Cl so CH ₂ COOH 46 Cl H CF ₃ H F Cl S COOH 47 Cl CF ₃ H F Cl S CH ₃ H CHCOOCHO I 48 Cl CF ₃ H F Cl S CH ₃ H CH ₂ CH ₂ COOH 49 Cl H CF ₃ H F Cl S CH ₂ CH ₂ COOCH ₃ 46 50 Cl H CF ₃ H F Cl S CHCOOC ₂ H ₅ 51 Cl CF ₃ H Cl Cl S CH ₃ H CH ₂ CH ₂ COOCH ₃ 52 Cl H CF ₃ H Cl Cl O CHCOOH 99 53 Cl CF ₃ H Cl Cl S CH ₃

Le a 26

- 46 Table 3 - continued

Example »* - Melting No. R ¹ R ² R ³ R ⁴ R ⁵ XYZ point ( ⁰ C)

54 Cl H CF ₃ H Cl Cl S CH ₂ CH ₂ COOH 85

55 Cl H CF ₃ H Cl Cl S CH ₂ CH ₂ COOCH ₃ 56 Cl H CF ₃ H Cl Cl S CN (C ₂ H ₅ ) ₂

S 57 Cl H CF ₃ H Cl Cl S CHCOOCH ₃

CH ₃ 58 Cl H CF ₃ M Cl Cl SO CH ₂ COOCH ₃

59 Cl H CF ₃ H Cl Cl SO CH ₂ CH ₂ OH 126

60 Cl H CF ₃ H Cl Cl S CH ₂ COOC ₃ H ₇

61 Cl H CF ₃ H Cl Cl S CH ₂ COOCH (CH ₃ ) ₂ 68 * ^U 62 Cl H CF ₃ H Cl Cl S CH ₂ COOC ₄ H ₉

63 Cl H CF ₃ H Cl Cl S CH ₂ COOCH ₂ CH (CH ₃ ) ₂

64 Cl H CF ₃ H Cl Cl O CH ₂ COOCH ₃

65 Cl H CF ₃ H Cl Cl 0 CHCOOCH ₃ I

CH ₃

66 Cl H CF ₃ HF Cl SO ₂ CHCOOC ₂ H ₅ 96

CH ₃ 67 Cl H CF ₃ HF Cl SO ₂ CH ₂ CH ₂ COOC ₂ H ₅ 100

*) The! N NMR spectra were recorded in CDCl ₃ with tetramethylsilane as the internal standard. The chemical shifts are usually given as 6 values for the grouping -CH ₂ -.

Le A 26 083 - Au8land

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The preparation of the compound listed in Table 3 as Example 40 is described by way of example below.

CH ₂ -SO-CH ₂ COOCh ₃

V "V ß '

(Method (c))

A solution of 1.6 g (9.3 mmol) of 3-chloroperbenzoic acid in 30 ml of chloroform is added to a cooled to -10 ⁰ C solution of 3.8 g (8.6 mmol) of 5- (2-CIilor- Methyl 5- (2-chloro-6-fluoro-4-trifluoromethyl-phenoxy) -benzyl) -mercaptoacetic acid in 25 ml of chloroform with stirring

added dropwise «The reaction mixture is stirred for 3 hours at -10 ⁰ C and 4 hours at +5 ⁰ C« For workup is shaken with 5Xiger sodium bicarbonate solution, the organic phase separated, dried with magnesium sulfate and filtered. The solvent is carefully distilled off from the filtrate in a water jet vacuum. 3.4 g (86 × of theory; 5- (2-chloro-5- (2-chloro-6-fluoro-4-rifluoromethyl-phenoxy) -benzyl) are obtained; Sulfinylessigsäuremethylester as crystalline

Residue of melting point 82 ° C.30

Le a 26 083 - abroad

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Application examples 5

In the following application examples, the compound shown below is used as a reference substance

used! 10

Cl COOCH ₃

₅ , (A)

15 3- (2 »4-dichloro-phenoxy) -6-nitrobenzoic acid methyl ester (known from US-PS 36 52 645 and US-PS 3,776,715).

Le A 26 083 · abroad

ίο

- 49 -

Example A Post-emergence test Solvent 5 parts by weight of acetone Emulsifier I 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound with the stated amount of solvent ι is the specified amount of emulsifier and dilute the concentrate with water to the desired concentration »

With the preparation of active compound injected test plants "which have a height of 5 - 15 cm so that the respective desired amounts of active ingredient per unit area are applied" The concentration of the spray mixture is so

kind

chosen "that in 2000 1 water / ha the respective desired amounts of active substance are applied" After three weeks the damage degree of the plants is rated in X damage in comparison to the development of the untreated control "means:

OX = no effect (as untreated control) 100 X = total destruction

In this test, for example, the compounds according to Preparation Examples (2) "(3) and (4) show significantly greater activity against weeds with good selectivity in wheat" such as "Datura" purslane "Sinapis and Solanum" than the reference substance (A ) "

35

Le A 26 083 - Foreign countries

Claims (3)

claims 1 * Herbicidal agent, characterized by a content of at least one halogen-substituted phenoxybenzyl (thi) ol derivative of the general formula (I), CH ₂ -YZ (D in which R is hydrogen, halogen, cyano or trifluoro-methyl, R * "stands for hydrogen or halogen" R is halogen, cyano, trifluoromethyl "trifluoromethoxy or trifluoromethylsulfonyl" R stands for hydrogen or halogen, R "stands for hydrogen or halogen" with the proviso that at least two of the substituents R, R, R and R are different from hydrogen, X door is halogen « Y is oxygen, sulfur, sulfinyl or sulfonyl and - 51 - Z is hydrogen »for optionally substituted by cyano» halogen, hydroxy »alkoxy» alkylthio, carboxy »alkoxycarbonyl» alkylcarbonyloxy or alkoxycarbonylalkoxycarbonyi substituted alkyl »each optionally substituted by halogen and / or alkyl cycloalkyl or cycloalkylalkyl» for each given if halogen-substituted alkenyl or alkynyl »or one of the following groups _Q l _Q 2 1 "2 ^Il VZ ¹ , -cz ² , wherein
20 m stands for the numbers 0 »1» 2 or 3 » Q ¹ and Q ² each for oxygen or sulfur stand"
25 Z ^{1 is} in each case optionally substituted by halogen »cyano, nitro» alkyl »haloalkyl, alkoxy» haloalkoxy »alkylthio» haloalkylthio »dialkylamino» carboxy and / or alkoxycarbonyl-substituted phenyl or naphthyl, or an optionally substituted by halogen and / or alkyl heterocyclic moiety from the series furyl »tetrahydrofuryl» oxotetrahydrofuryl »thionyl, tetrahydrothienyl» perhydropyranyl »oxazolyl» thiazolyl, Thiadiazolyl, dioxolanyl, perhydropyrrolyl, Le A 26 083 · abroad - 52 - Oxoperhydropyrrolyl, pyridinyl or pyrimidinyl, ο
Z is hydrogen, alkyl optionally substituted by halogen, alkoxy or alkoxycarbonyl, optionally substituted by halogen and / or alkyl cycloalkyl, alkenyl, benzyl or optionally by halogen, cyano, nitro, alkyl, haloalcyl, alkoxy, haloalkoxy, alkylthio, Haloalkylthio and / or alkoxycarbonyl is substituted phenyl, alkoxy, benzyloxy, phenoxy, alkylthio, benzylthio, phenylthio or dialkylamino, and Z and Z are each optionally halogen-substituted alkyl or alkoxy, in addition to extenders and / or surface-active substances. 2. A herbicidal composition according to claim 1, characterized by a content of a compound of general formula (I), wherein R is hydrogen, fluorine, chlorine, brora, cyano or trifluoroethyl, R is hydrogen, fluorine, chlorine or bromine, R is fluorine, chlorine, bromine, cyano, trifluoromethyl, trifluoromethoxy or trifluoromethylsulfonyl. - 53 - R ^{4 is} hydrogen, fluorine, chlorine or bromine, R ^{5 is} hydrogen, fluorine, chlorine or bromine. with the proviso that at least two of the substituents R ¹ , R ² , R ⁴ and R ⁵ are different from hydrogen - X is fluorine, chlorine or bromine, Y is oxygen, sulfur, sulfinyl or sulfonyl and Z is hydrogen, where appropriate by cyano, fluorine, chlorine, bromine, hydroxy, C ₁ -C ₆ - Alkoxy, C ₁ -C ₆ -alkylthio, carboxy, C ₁ -C ₆ -alklene carboxy-carbonyl, C ₁ -C ₆ -alkyl-carbonyloxy or CJ ₁ -C ₆ -alkoxycarbonyl-C ₁ -C ₆ -alkoxycarbonyl-substituted C ₁ -C ₆ -alkyl, in each case optionally by fluorine, chlorine, Bromine and / or C ₁ -C ₄ -A ^ yI substituted C ₃ -C ₈ cycloalkyl or C ₃ -C ₈ -cycloalkyl-C ₁ -C ₄ -alkyl, in each case optionally substituted by fluorine, chlorine and / or bromine-substituted C ₃ -C ₆ -alkenyl or C ₃ -C ₆ -alkynyl, or for one of the following Groupings stands Q * ² 1 2 wherein
35 m stands for the numbers 0, 1, 2 or 3, Le A 26 063 - Auslanc - 54 - Q ¹ and Q ² stand for oxygen or sulfur, respectively « Z ^{1 is} in each case optionally substituted by fluorine "chlorine" bromine "iodo, cyano" nitro, C 1 -C ₄ -alkyl, fluorine-substituted and / or chlorine-substituted C ₁ -C ₂ -AlKyI, C ₁ -Q ₄ -alkoxy, fluorine-substituted and / or chlorine-substituted C ₁ -C ₂ -alkoxy, C ₁ -C ₄ -alkylthio, fluoro-substituted and / or chlorine-substituted C ₁ -C ₂ -alkylthio, di- (C ₁ -CG-alkyl) -amino, carboxy and / or C ₁ -C ₄ -alkoxycarbonyl-substituted phenyl or naph- thyl "or an optionally substituted by fluorine" chlorine "bromine and / or C ₁ -C ₄ -AlKyI heterocyclic moiety from the series furyl, tetrahydrofuryl« Oxotetrahydrofuryl, thienyl, tetrahydrothienyl, perhydropy- ranyl, oxazolyl, thiazolyl, thiadiazolyl, dioxolanyl, perhydropyrrolyl, oxoperhydropyrrolyl, pyridinyl or pyrimidinyl, Z ^{2 is} hydrogen, for optionally by Fluorine, chlorine, bromine, C ₁ -C ₄ -alkoxy or C ₁ -C ₄ -alkoxycarbonyl-substituted C ₁ -C ₆ -alkyl, optionally substituted by fluorine, chlorine, bromine and / or C ₁ -C ₄ - AlKyI substituted C ₃ -C ₆ - Cycloalkyl, for C ₃ -C ₆ alkenyl, benzyl or for optionally substituted by fluorine, chlorine, bromine, iodine, cyano, nitro, C ₁ -C ₄ -alkyl, fluoro-substituted and / or chlorine-substituted C ₁ -C ₂ -alkyl "C ₁ -C ₄ -alkoxy, fluorine-substituted and / or chlorine-substituted Le A 26 083 '« - 55 - substituted C ₁ -C ₃ -alkoxy, C ₁ -C ₄ -alkylthio, fluoro-substituted and / or chlorine-substituted C ₁ -C ₄ -alkylthio and / or C ₁ -C ₄ -alkoxycarbonyl-substituted phenyl, for C ₁ -C _4- alkoxy, benzyloxy. Phenoxy, Cj-C ^ alkylthio, benzylthio, phenylthio or di (C ₁ -C ₄ alkyl) -amino, and Z and Z are each optionally fluorine and / or chlorine-substituted C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy. 3. A herbicidal composition according to claim 1, characterized by a content of a compound of general formula (I), wherein
R ^{1 is} chlorine, R is hydrogen, R ^{3 is} trifluoromethyl, R is hydrogen, fluorine or chlorine, R ^{5 is} T'luor or chlorine, X is chlorine or bromine, Y is oxygen, sulfur, sulfinyl or sulfonyl and Z is hydrogen, optionally substituted by cyano, fluorine, chlorine, hydroxy, C ₁ -C ₄ -alkoxy, 2 8 3/57 - 56 - C ₁ -C ₄ -alkylthio, carboxy-C ₁ -C ₄ -alkoxy-carbonyl, C ₁ -C ₄ -alkylcarbonyloxy or C ₁ -C ₄ -alkoxy-carbonyl C ₁ -C ₂ -alkoxycarbonyl-substituted C ₁ -C ₄ -alkyl- AlKyI, in each case optionally substituted by chlorine and / or methyl-substituted C ₃ -C _£) -cycloalkyl or C ₃ -C ₆ -cycloalkyl-C ₁ -C ₂ -slkyl »in each case optionally substituted by chlorine C ₃ -C 4" alkenyl or C ₃ -C 1 -alkynyl, or for one of the following groups Q ¹ Q ²
B I ' wherein
m is the numbers 0, 1 or 2, Q ¹ and Q ^{2 are} each oxygen or sulfur, Z ^{1 is} in each case optionally substituted by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, difluoromethylthio, trifluoromethylthio, dimethylamines »and / or methoxycarbonyl-substituted phenyl or naphthyl, which is a heterocyclic group optionally substituted by chlorine and / or methyl from the series furyl, tetrahydrofuryl, thionyl, perhydropyranyl, Oxazolyl, thiazolyl or dioxolanyl, Le A 26 083 - Foreign countries 2 ^ 3757 - 57 - Z ^{2 is} hydrogen, optionally substituted by B is fluorine, chlorine, C ₁ -C ₂ -alkoxy or C ₁ -C ₂ -alkoxy carbonyl-substituted C ₁ -C ₄ -alkyl, for C ₃ -C ₆ -cycloalkyl optionally substituted by chlorine and / or methyl, for C ₃ -C ₄ -alkyl-iodo, benzyl, optionally by fluorine, chlorine, bromine , Nitro, methyl, ethyl, trifluoromethyl, Methoxy, ethoxy, difluoromethoxy, trifluoromethoxy and / or msthoxycarbonyl substituted phenyl or represents dimethylamines, and Z ³ and Z ^{4 are} each C ₁ -C ₃ -alkoxy, 4 · Process for the Preparation of Halogen-Substituted Phenoxybenzyl (thio) ol Derivatives of the General Formula (I)
20 (I) ^R1 is hydrogen, halogen, or trifluoromethyl Cyeno, R ^{2 is} hydrogen or halogen, 30 R ^{3 is} halogen, cyano, trifluoromethyl, trifluoromethoxy or trifluoromethylsulfonyl, R ^{4 is} hydrogen or halogen, 35  ,Foreign countries - 58 - R ^{5 is} hydrogen or halogen, 5 with the proviso that at least two of the substituents R ¹ , R ² , R ⁴ and R ⁵ are different from hydrogen, X stands for halogen ', Y represents oxygen, sulfur, sulfinyl or sulfonyl and Z is hydrogen, optionally by Cyano, halogen, hydroxy, alkoxy, alkylthio, carboxy, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonylalkoxycarbonyl-substituted alkyl, in each case optionally halogen- and / or alkyl-substituted cycloalkyl or cycloalkylalkyl, in each case optionally halogen-substituted alkenyl or alkynyl, or represents the grouping below Q ¹ Q ² Ι i ^| -CZ ² , -P ^Vorin m is the numbers O, 1, 2 or 3, Q ¹ and Q ^{2 are} each oxygen or sulfur, Le A 26 083 - - 59 - Z ^{1 is} in each case optionally substituted by halogen, cyano "nitro, alkyl" haloalkyl, alkoxy, Haloalkoxy, alkylthio «haloalkylthio, dialkylamino, carboxy and / or alkoxycarbonyl-substituted phenyl or naphthyl, or represents an optionally halogen and / or Alkyl substituted heterocyclic group Furyl, Tatrahydrofuryl, Oxotetrahydrofuryl, Thionyl, Tetrahydrothienyl, Perhydropyranyl, Oxazolyl, Thiazolyl, Thiadiazolyl, Oioxolanyl, Parhydropyrrolyl, Oxoperhydropyrrolyl, Pyridinyl vider Pyrimi- dinyl stands, Z ^{2 is} hydrogen, alkyl optionally substituted by halogen, alkoxy or alkoxycarbonyl, optionally by halogen and / or alkyl-substituted cycloalkyl, alkenyl-benzyl, or optionally substituted by halo-cyano-nitro, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio and / or alkoxycarbonyl Phenyl, alkoxy, benzyloxy, phenoxy, alkylthio, "benzylthio," phenylthio or dialkylamino "and Z ³ and Z * are each optionally halogen substituted alkyl or alkoxy. characterized in that «one A 26 083. abroad - 60 - (a) Halogen-substituted Phenoxyuenzylhalogenide the allpeme'nen formula (II) R ² R ¹ CH ₂ -X ¹ in walcher R ¹ , R ² , R ³ , R ⁴ , R ⁵ and X have the meanings given in claim 1 and 15 X ^{1 is} halogen, with nucleophilic compounds of the general Formula (III) 20 M-Y-Z (III) in which Y and Z have the meanings given above and M is hydrogen , sodium or potassium is standing, 30 if appropriate in the presence of acid reactors and if appropriate in the presence of diluents, of which Le a 26 083 - abroad - 61 - (b) halogen-substituted phenoxybenzylthiols of the general formula (Ia) R ² R ¹ CH ₂ -YH in which R ¹ , E ^? ' _t P ³ , R ⁴ , R ⁵ , X and Y have the meanings given in claim 1 with electrophilic compounds of the general formula (IV) X ² - Z (IV) 20 in which Z has the meaning given in claim 1 and 25 X ^{2 stands} for a nucleophilic gangue group » optionally in the presence of acid acceptors and optionally in Qegsnvart of diluents, or that (c) Halogen-substituted phenoxybenzylthiol derivatives of the general formula (Ib) Le a 26 083 - abroad - 62 - CH ₂ -SZ in which 1 2 3 4 5 ' R ♦ R, R «R, R, X and Z have the meanings given above« with oxidizing agents, if appropriate in the presence of diluents.