DE3101544A1 - Quinolinoxyphenoxypropionic acid derivatives, their preparation, and their use as herbicides - Google Patents

Abstract

Quinolinoxyphenoxypropionic acids of the formula <IMAGE> in which one of the radicals R<1> or R<3> is a group of the formula <IMAGE> and the other radical is H, alkyl, phenyl, Cl or Br; R<2> is H, alkyl, Cl, Br, CN or COO(C1-C4)-alkyl; R<4> is H, alkyl, alkoxy, dialkylamino, NO2, CF3 or halogen, n is 1 or 2, or (in the event that R<2> NOTEQUAL H), O and Z also represent a carboxyl, carboxylate, carbonate, thiocarbonate, (substituted)carboxamide, thioamide, (substituted)carbohydrazide or nitrile group, are effective herbicides.

Description

"· -» -tr _-, ■ - ■> OO

HOECHST AKTIENGESELLSCHAFT HOE 81 / F 011 Dr.TG/mh

Quinolinoxy-phenoxypropionic acid derivatives, process for their preparation and their use as herbicides

The invention relates to quinolinoxyphenoxypropionic acid derivatives of formula I.

(I)

in which one of the radicals R or R, preferably R is a group of the formula II

- 0- (C jV-OCH - Z

and the other is hydrogen, (C ₁ -Cw) -AIlCyI, phenyl, chlorine or bromine,

R ^{2 is} hydrogen, (Cj-C ^ -alkyl, chlorine, bromine, CN or COO (C ₁ -C _{l (} ) -alkyl _f

R ^{4 is} hydrogen, (C ₁ -C ₂₁ ) -alkyl, (C ₁ -C ^) -AlkOXy, di- (C ₁ -C alkylaraino, nitro, trifluoroethyl or halogen,

2 η 1 or 2, as well as in the event that R is hydrogen

is different, also 0, Z is a radical of the formula

-COOR ₅ , -COSR ₆ , -CONC ^ e, -CSNH ₂ ,

R ⁹

, 10

-CON - Nrr ^ 1 1 or CN,

R ^{5 is} hydrogen, (Cj-C ₁₂ ) -alkyl » ^d as optionally through 1-6 halogen atoms, preferably F, Cl, Br and / or through OH, (C ₁ -Cg) -AlkOXy, (Cj-C ^ -alkylthio , (C ₁ -Cg) -alkoxy-tCj-CgJ-alkoxy, halogen- (C ₁ -C ₂ ) -alkoxy, methoxyethoxy-ethoxy, (C ₁ -C ₄ ) -alkylamino, di- (C ₁ -C ^ ) -alkylamino, phenyl, oxiranyl and phenoxy, the latter also being able to be substituted one to two _{times by halogen or (C 1} -Cn) -alkyl; (C ₁₅ -Cg) -cycloalkyl or halogen- (C ₅ -Cg ) -alkyl; (C ₃ -Cg) -alkenyl, halogen- (Co-Cg) -alkenyl or (Cc-Cg) -cycloalkenyl; (Co-C ^) -alkynyl, which is optionally substituted once or twice by (C ₁ -Cg) -alkyl, phenyl, halogen or (C ^ C ^ -alkoxy is substituted;
Phenyl which is optionally substituted one to three times by (Cj-C ^ J-alkyl, (C ₁ -C ₁ ^) -AlkOXy, halogen, nitro or trifluoromethyl;
Furfuryl, tetrahydrofurfuryl;
Remnants of the formulas

.R ¹² R ¹⁴ R ¹⁴

-N = C, -C- COOR ¹⁶ or -C-CN, or

13th

a cation equivalent of an organic or inorganic base:

R (Cj-CGJ-alkyl which is optionally substituted by (C ₁ -C ₁ P-alkoxy, halogen or phenyl, the latter may also be substituted one to three times by (C.-C _ü) alkyl or halogen; (C -, - Cg) -alkenyl or phenyl, which is optionally substituted one to three times by (C.-Cjj) -alkyl and / or halogen; 8

R and R can be identical or different and are hydrogen, (C ₁ -Cg) -AIkYl, hydroxy-tCj-CgJ-alkyl, (C ₅ -C ₆ ) -cycloalkyl or phenyl, which is optionally substituted one to three times by (CpC ^ -Alkyl, (C, -C ₄ ) -alkoxy, halogen or trifluoromethyl is substituted (with the proviso that R ⁷ and R are not phenyl together) or together

10, 11

with a nitrogen atom denote a pyrrolidino, piperidino or morpholino radical,
Hydrogen or methyl;
Hydrogen, methyl or ethyl;

R is hydrogen, methyl, ethyl or phenyl;

R ¹² and R ¹³ (C ₁ -Cu) -AIlCyI and

14 15

R and R ^{J are} hydrogen or methyl, as well as

, 16

Signify hydrogen, (C.-C ₁ ^) - alkyl or a cation equivalent of an inorganic or organic acid.

In the above, “halogen” preferably means chlorine and bromine. Under "cation equivalent of an inorganic or organic Base "is preferably understood to mean ammonium, alkali metal or alkaline earth metal cations or those of nitrogen-containing organic cations Bases such as pyridine, triethylamine, hydroxyethylamine or tris-hydroxyethylamine.

The compounds of general formula I, in which one

Ί ο -ι

the radical R or R, preferably R, denotes the radical of the formula II, can be identified in a manner known per se from known or produce starting materials produced by known processes.

25 30

These processes are characterized in that one

a) compounds of formula I.

(I)

in which one of the radicals R or R, preferably R, denotes a halogen atom, with compounds of the formula (III '

CH,

OCH - Z

wherein Z has the meaning given above, converts,

(III)

b) compounds of formula I.

(D

I'D I

in which one of the radicals R or R, preferably P., a Remainder of formula IV

(IV)

carries, with compounds of the formula V.

CH3 A-CH-Z

(V)

in which A is halogen or a sulfoester group, e.g. the mesyl or represents a tosyl radical and Z has the meaning given above, and, if desired, reacted

c) the compounds obtained according to a) and b) by saponification, salt formation, esterification, transesterification, amidation, Elimination or addition of water or addition of hydrogen sulfide converted into other compounds of the formula I according to the invention.

By using optically active starting materials of the formula III and V, the D- and L-enantiomers of Compounds of the formula I, in which the OC-C atom of the propionate residue is the chiral center.

The D-forms, the corresponding ones, are of particular importance here Outperform racemates in herbicidal effectiveness.

The D compounds are obtained by adding D-2- (4-hydroxyphenoxy) propionic acid derivatives (D-III) or L-propionic acid derivatives (D-V) as reactants for the compounds of Formula I with the radicals R or R ^ = halogen or R or fP = remainder of the formula IV used:

CH.

(D-III)

IH

CH ₃ (DV)

The reactions of compounds of the formula I with the radicals R or R ^ = halogen with compounds of the formula III (D-III) and of compounds of the formula I which carry the radicals R or R-> = formula IV with compounds of the formula V (DV) can be carried out in protic or aprotic solvents (for example water, dimethylformamide, dimethyl sulfoxide, sulfolane, N-methylpyrrolidone, hexamethylphosphoric triamide, acetonitrile, acetone, methyl ethyl ketone, benzene, toluene, xylene, chlorobenzene, o-dichlorobenzene, with either the salts of III or the compounds of the formula I in which the radicals R or R ^ carry the radical of the formula IV are used or the free phenols are used inorganic or organic bases such as metal alcoholates !!, tertiary amines, alkali or alkaline earth carbonates, NaH or alkalis (NaOH, KOH) to trap the free acids formed n are between 30 and 250 ^° C. or the boiling point of the solvents used and can be varied within wide limits. Is preferably carried out at 90 to 16O ⁰ C. The starting materials of formula I

3 Ί Ο 1 5 4 4

wherein the radicals R or R ^ carry the radical of the formula IV, can be in a simple manner, by reacting compounds of the formula I with d
genes with hydroquinone.

Compounds of the formula I with the radicals R or R- * = Halo-

To c)

For amidation of compounds of the formula I with the radicals 1 3

R or R ^{J of} the formula II can either start from esters and react these with amines, ammonia or hydrazines.

The same solvents are preferably used as in a) and temperatures between 40 ° C. and the reflux temperature are used. But you can also first convert acids of the formula I with the radicals R or R- ^ of the formula II in a known manner into acid halides and then react these with ammonia, amines or hydrazines. An at least one molar excess of the base used is required to bind the hydrogen halide released. Other esters or thioesters of the formula I can be obtained by reacting the acid chloride with alcohols or mercaptans. The transesterification takes place through acidic or basic catalysis. The alcohol to be introduced into the ester is expediently added in excess and the lower-boiling alcohol released is continuously distilled off to the extent that it is formed during the transesterification. In the dehydration of amides to nitriles, aromatic hydrocarbons are preferably used at temperatures from 50 ^° C. to the boiling point. The subsequent addition of HpS for the manufacture of thioamides (Z = CSNHp) is expediently carried out in an autoclave in the presence of catalytic amounts of a base (preferably ethanolamine) at temperatures between 50 and 15O ⁰ C. oxime ester of the form

^ R ¹²
mel I (Z = COO - N = CCLq13 is obtained by conversion

of the corresponding acid halides of the formula I with the radicals R or R of the formula II (Z = COHaI) with oximes. 35

If necessary, they can be combined with other herbicides, insecticides and fungicides. For example, you can use the

Vegetable and sugar beet cultivation, in fruit and ornamental plant cultivation as well as in plantations, tree nurseries and young forest plantings to control weed grasses. Also for They can be used to keep roadsides, railway embankments, etc. free.

The quinoline compounds according to the invention are distinguished in Used pre-emergence and especially post-emergence due to a strong selective herbicidal effect against annual and perennial grass-like weeds in dicotyledonous and - in some cases - monocotyledonous crops. Even in In high dosages, the agents are compatible with many important cultivated plants. They are therefore suitable as selective herbicides in agricultural, forestry and horticultural crops.

In low doses, specific effects are observed which enable use as plant growth regulators. The agents contain the active ingredients of the formula I.

1 λ
with the radicals R or R of the formula II in general from 2 to 95% by weight. They can be used as wettable powders, emulsifiable concentrates, sprayable solutions. Dusts or granules are used in the usual preparations.

Wettable powders are preparations that are uniformly dispersible in water and contain, in addition to the active ingredient, a diluent or an inert substance, as well as wetting agents. eg polyoxyethylated alkylphenols, polyoxyethylated oleyl-, stearylamines, alkyl- or alkylphenylsulfonates and dispersants, e.g. lign? - ■ .- Sodium sulfonic acid, 2,2'-dinaphthylmethane-6,6'-disul. contain sodium or oleylmethyltaurine.

Emulsifiable concentrates are made by dissolving the active ingredient in an organic solvent, e.g. butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling solvents

BAD ORiG / NAL

Aromatics and addition of a nonionic wetting agent, for example a polyoxyethylated oleyl or stearylamine, obtain.

Dust is obtained by grinding the active ingredient finely divided solid substances, e.g. talc, natural clays such as kaolin, bentonite, pyrophillite or diatomaceous earth.

Granules can either be produced by spraying the active ingredient onto adsorptive, granulated inert material or by applying active ingredient concentrates using adhesives, e.g. polyvinyl alcohol, polyacrylic acid Sodium or mineral oils on the surface of carrier materials such as sand, kaolinite or granulated inert material. Suitable active ingredients can also be used in the manner customary for the production of fertilizer granules - if desired in mixture with fertilizers - are produced.

In the case of the herbicidal compositions, the concentrations of the active compounds in the customary formulations can be different. In wettable powders, the active ingredient concentration varies, for example, between about 10 % and 95 %, the remainder being made up of the formulation additives given above. In the case of emulsifiable concentrates, the active ingredient concentration is around 10 % to 80 %. Dust-like formulations usually contain 5 to 20 % active ingredient, sprayable solutions around 2 to 20 %. In the case of granules, the active ingredient content depends in part on whether the active compound is liquid or solid and which granulation auxiliaries, fillers, etc. are used.

The commercially available concentrates are optionally used for use diluted in the usual way, e.g. in the case of wettable powders and emulsifiable concentrates with water. Dust-like and granulated preparations as well as sprayable solutions are no longer treated with extensive

diluted with other inert substances. With the external conditions such as temperature, humidity, etc., the required application rate varies. It can fluctuate within wide limits, e.g. between 0.05 and 10.0 kg / ha or more active substance, but preferably it is between 0.1 and 5 kg / ha.

Manufacturing examples:
example 1

2 ~ /] \ ~ (6-Methy ich inolyD-2-oxy-phenoxy / - propionic acid ethyl ester

21 g (0.1 mol) of ethyl 2- (4-hydroxyphenoxy) propionate are added dropwise to 2.9 g of NaH (80% strength in oil) in 100 ml of absolute dimethylformamide under a nitrogen atmosphere. Is allowed to react until no more H ₂ escapes, then added 17.7 g (0.1 mole) of 6-methyl-2-chloroquinoline and stir for 2 hours at 100 ⁰ C. The progress of the reaction is controlled by thin layer chromatography. After the reaction has ended, the mixture is cooled, filtered and the filtrate is largely concentrated in vacuo. The residue is taken up in chloroform, filtered through a short layer of silica gel and the solution is evaporated in vacuo. 30.7 g (89.2 % of theory) of the pure product are obtained, n ^: 1.5853.

Example 2

2 »/ ^I f- (8-Isopropylquinolyl) -4-oxy-phenoxy7-propionic acid ethyl ester

21 g (0.1 mol) of ethyl 2- (4-hydroxyphenoxy) propionate are added dropwise to 2.9 g of NaH (80 % in oil) in 100 ml of absolute dimethylformamide under a nitrogen atmosphere. Is allowed to react, then adding 20.5 g (0.1 mol) of 8-isopropyl-4-chloroquinoline and stirred for 3 hours at 100 ⁰ C. The mixture is worked as described in Example. 1 35 g (92.5 % of theory) of the product are obtained, n ^ ⁵ : 1.5641.

Similarly, the following were produced:

Ex.
No. H R ¹ 2 ^H 5 r3 R ² <»\ Phys.
data : 1.6001 10 3 H CH,
-OCHCOOC .H H 8-NO ₂ 4 ⁵ : 65 ⁰ C 4th H It H H 5-NO ₂ Fp. -.1.5849 15th 5 CH ₃ ti CH ₃ H 7-Cl : 1.5798 6th H Il H H' 8-CH ₃ : 7O ⁰ C 20th . 7th ^C 6 ^H 5 It H Br • H Fp. : 1.5920 8th Il Cl H H " ³ D ⁵ : 1.5963 9 ~ ° \ C CH ₃
JV0CHC00C ₂ H ₅
J H . 8-Cl 4 ⁵ : 1.5857 25th 10 It H H 4 ⁵ : 1.5818 11 It ^C 6 ^H 5 7-CF ₃ : 103 ° C 30th 12th Il Cl 6.8-Cl Fp. : 1.5915 13th ti H 7-Cl 4 ⁵ 14th It H H oil

16

H 7-CF ₃ m.p .: 73 "CH 6 _{-C 3} H ₇ (I) n ^ ⁵ : 1.5744

Analogously, ^{1 is} obtained:

, 3

, 2

CHo

I J

OCH - Z

Tabel:

Example no.

Phys. data

17 18 19 20 21

22nd

23 24

26 27 28 29

30th

31 32 33 34 35

H H H H

H H

H H H H

H H H H H

H H H H H

H H

H- H

H H H H

H H

H H H H H

7-CH ₃ -COOCH ₂ CH ₂ OCH ₃

7-CH ₃ -COOCH ₂ CH ₂ CH (CH ₃ ) -OCH ₃

7-CH ₃ -COOCH ₂ CH ₂ Ch ₂ -Cl

7-CH ₃ -COOCH ₂ -CH = CH ₂

7-CH ₃ -COOCH ₂ -C ^ CH

7-CH ₀ -COO-

7-CH ₃ • -COOCH ₂ -COOCh ₃

7-CH ₃ -COOCH (CH ₃ ) -COOC ₄ H _{g (n)}

7-CH

7-CH 7-CH T-CH

-COSC ₂ H ₅

-CONH ₂

-CONHC ₂ H ₅

7-CH- -CON (CHo)

7-CH ₀ -CON

7-CH ₃ -COOH

7-CH ₃ -COONa

7-CH ₃ -COOK

7-CH ₃ -COO-N = C (CH _{3) 2}

7-CH _Q -CS-NH ₀

Formulation examples: Example A.

An emulsifiable concentrate is obtained from 15 parts by weight of active ingredient of general formula I with

the radicals R or -R of the formula II 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of ethoxylated nonylphenol (10 AeO) as 'Emulsifier.

Example B.

A wettable powder which is easily dispersible in water is obtained by

25 parts by weight of active ingredient of general formula I with

the radicals R or R of the formula II 64 parts by weight of kaolin-containing quartz as an inert substance 10 parts by weight of potassium lignosulfonate and 1 part by weight of sodium oleylmethyltaurate as wetting agent

and dispersant mixes and grinds in a pin mill.

Example C
25th

A dust is obtained by adding 10 parts by weight of active ingredient of general formula I

1 3 the radicals R or R of the formula II

and 90 parts by weight of talc as an inert substance and comminuted in a hammer mill.

Example D

A granulate consists, for example, of about 2 to 15 parts by weight of the active ingredient of the general formula I.

with the Rf formula II

1 λ with the radicals R or R the

85 to 98 parts by weight of inert granulate materials, such as

e.g. attapulgite, pumice stone and quartz sand.

Biological examples

1. Pre-emergence effect

Seeds of various economically important weeds and grass weeds were placed in pots with sandy loam soil sown and covered with covering soil. The compounds of the invention formulated as wettable powders were in the form of aqueous suspensions or emulsions with a water application rate of 600 l / ha then on the Sprayed the surface of the earth. The pots were then placed in the greenhouse and the test plants under cultivated in good growing conditions. After about 3 weeks, the plant damage was assessed visually. The damage or death caused by the test preparations was in percent compared to untreated Plants captured.

The results of these experiments (Table 1) show that the compounds according to the invention at doses of 2.4 kg AS / ha destroy economically important grass weeds, while dicotyledonous plants are completely spared will. The damage to the test plants is given in the following key:

0 = without damage

1 = 0-20 % damage

2 = 20-40% damage
3 = 40-60 % damage

4 = 60-80 % damage

5 = 80-100 % damage

Table 1:

Herbicidal effectiveness against grasses and weeds in pre-emergence
5

Compound dose AVF ALM SAL LOM ECG SIA STM kg AS / ha

according to spec. 1 2.4 4 4 5 5 5 0 0

Abbreviations:

AVF = wild oats ECG = chicken millet

ALM = field foxtail SIA = field mustard

SAL = millet STM = chickweed

LOM = ryegrass AS = active ingredient 15

2. Post-emergence effect

Various economically important weeds and weeds were sown in pots with sandy loam and under greenhouse conditions up to the three-leaf stage of the grasses (a total of 3 weeks). The compounds according to the invention were then used as aqueous Dilutions of £ 20 wettable powders on the plant material applied, the volume of the spray liquor corresponding to an amount of the equivalent of 600 l / ha. the Plants were placed under greenhouse conditions and rated visually for harmful effects about 3 weeks later.

As can be seen from Table 2, those according to the invention are suitable Post-emergence compounds help destroy unwanted grass grass, while dicotyledon plants do not or only marginally damaged. ·

¹ ^ AO «· A

Table 2:

Herbicidal effectiveness against grasses and weeds in the Post-emergence

Compound dose SAL LOM ECG CRS STM kg AS / ha ___

according to spec. 1 2.4

SAL = Bristle Millet LOM = Raygrass ECG = Chicken Millet

CRS = Saatwucherblurae STM = Vogelraiere AS = active ingredient

Claims (5)

310154Α HOE 81 / F .Q1.1 Claims: 1. Compounds of formula I (I) in which one of the radicals R or R, preferably R is a group of the formula II CH (ID _ ο - <(ϊ W OCH - Z and the other hydrogen, (C-C ^) - AIkVl, phenyl, Is chlorine or bromine, R is hydrogen, (Cj-C ^) - alkyl, chlorine, bromine, CN or R is hydrogen, (C, -C ₄ ) -alkyl, (C ₁ -C ₄ ) di- (C ₁ -C ₄ ) -alkylamino, nitro, trifluoromethyl or halogen, η 1 or 2, and in the event that R ^{2 is} different from hydrogen, also 0, Z is a radical of the formula 7th
-COOR ₅ , -COSR ₆ , -C0NCr8> -CSNH ₂ , R.
CON - N ^ "11 or CN, ~ K ~ ^ U ~ HOE 8i / F 011 R ^{5 represents} hydrogen, (CpC ^ -alkyl, which is optionally substituted by 1-6 halogen atoms, preferably F, Cl, Br and / or by OH, (C ₁ -Cg) -AIkOXy, (CpC ^ -alkylthio, (C.- Cg) -Alkoxy- (C.-Cg) -alkoxy, halogen- (C ₁ -C ₂ ) -alkoxy, methoxyethoxy-ethoxy, (CpC ^ i-alkylamino, di- (Cj-C ^) - alkylaraino, phenyl, Oxiranyl and phenoxy is substituted, the latter also being substituted one to two times by halogen or (C.-C ^) - alkyl; (C ₅ -Cg) -cycloalkyl or halo- (C ₅ -Cg) -alkyl; ( Co-Cg) -alkenyl, halogen- (C ^ -Cg) -alkenyl or (C ₅ -Cg) -cycloalkenyl; (Co-C ₁ ,) -alkynyl, which is optionally substituted once or twice by (C.-Cg) -Alkyl, phenyl, halogen or (C ₁ -Cp) -AIkOXy is substituted; phenyl, which is optionally substituted one to three times by (C - C ||) -alkyl, (C] -C ₁ J) -alkoxy, Halogen, nitro or trifluoromethyl is substituted;
Furfuryl, tetrahydrofurfaryl;
Remnants of the formulas / ^{r12 r14 r14} -N = C, - C - COOR ¹⁶ or -C-CN Or \ 13 »ις» ις RR ^ID R ^iD a cation equivalent of an organic or inorganic one Base; R (Cj-CgJ-alkyl, which is optionally _{substituted by (C 1} -C ₁₊ ) -alkoxy, halogen or phenyl, the latter also being mono- to trisubstituted by (C ₁ -C ₁ ) -alkyl or halogen (Co-Cg) -alkenyl or phenyl, which is optionally substituted one to three times by (Cj-C ^ -alkyl and / or halogen;
R. R and R can be identical or different and are hydrogen, (C ₁ -Cg) -AIlCyI, HyUrOXy- (C ₁ -Cg) -AIkYl, (C ₅ -Cg) -cycloalkyl or phenyl, which is optionally mono- to HOE 81 / F 011 R ^: triple by (C ₁ -C ₁₄ ) -alkyl, (CpC ^ -alkoxy, halogen or trifluoromethyl is substituted (with the proviso 7 8 that R and R are not phenyl together) or together with a nitrogen atom denote a pyrrolidino, piperidino or morpholino radical, Hydrogen or methyl; R is hydrogen, methyl or ethyl; , 11 Hydrogen, methyl, ethyl or phenyl; R ¹² and R ¹³ (C ₁ -C ₁₁ ) -alkyl and 14 ^1C
r ' ⁴ and R «16 Hydrogen or methyl, as well Signify hydrogen, (Cj-Cj ₁ ) -alkyl or a cation equivalent of an inorganic or organic acid. 2. Process for the preparation of compounds of the formula I, characterized in that one a) compounds of formula I. (I) -10 1 in which one of the radicals R or R, preferably R ', denotes a halogen atom, with compounds of the formula (III) (III) wherein Z has the meaning given above, converts, b) compounds of formula I. HOE 81 / F 011 (I) in which one of the radicals R or R, preferably R, is a radical of the formula IV (IV) carries, with compounds of the formula V. CH3 A-CH-Z (V) in which A is halogen or a sulfoester group, e.g. Represents mesyl or tosyl radical and Z has the meaning given above, reacted and, if desired c) the compounds obtained according to a) and b) by saponification, salt formation, esterification, transesterification, amidation, Elimination or addition of water or addition of hydrogen sulfide in other compounds of the formula I according to the invention in which one of the radicals R or R is preferred R, which carries the remainder of the formula II, is converted. 3 · Herbicidal agents, characterized by an effective Content of compounds of the formula I. 4. Use of compounds of the formula I for combating unwanted vegetation. 5. A method for controlling undesirable vegetation, characterized in that an effective amount of a Applying the compound of the formula I to the plants or the area overgrown by them.