CA1120034A - Phenoxy-phenoxy-propionic acid amides, process for their manufacture and their use as herbicides - Google Patents

Abstract

Abstract of the Disclosure:
The invention is concerned with phenoxy-phenoxy-pro-pionic acid amides of the formula

Description

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This invention relates to novel phenoxy-phenoxy-pro-pionic acid amides of the formula I

~- O ~NO 2 -CH-C~N
(R~ ) n CH3 O 3 in which R1 is halogen, ~ and/or CF3;

n is 1 or 2, R2 is hydrogen or (C1-CI~)alkyl;

R3 is (C3-C6)alkenyl, (C3-C6)alkinyl, hydroxy-(C1-C4)-alkyl9 (Cl-C4)alkoxy-(C1-C4)alkyl, di-~C1-C4)alkylamino-(C1-C4)alkyl, cyano-(C1-C4)alkyl, (C1-C4)alkylthio-(C1-C4)alkyl, (C5-C6)cycloalkyl, methyl-cyclohexyl, phenyl-(C1-C4~alkyl, pyridyl or pyrimidyl;
or R2 and R3 together form a 4 to 7-membered ring in which up to 2 carbon atoms can be replaced by N and/or O.
The compounds of the formula I according to the in-vention can be prepared by reacting phenoxy-phenoxy-pro-pionic acid halides of the formula II (method A~ or phenoxy-phenoxy-propionic acid~esters of the formula III
~method B) with corresponding amines of the formula IV

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- 3 - HOE 78/F 238 (R1 ) ~ ~ 2 ~-o-~-NO
O-CH-C-Hal n Cl 3 o O-CIH-~IC-OR

(II) CH3 o (III) . R = (C~-C8)-ALt~yl .' ~ ~ .

~ H-N ~IV) .~
(I) or by reacting substituted 3-hydroxy-4-nitro-diphenyl ethers with halopropionic acid amides (method C):

O ~ -N02 (V) + Hal-CH-CON \
n OH CH3 3 Method A) The reaction of the acid halides (II) with amines is preferably carried out in an inert organic such as, for example, methyl ethyl ketone, dimethoxyethane, benzene, toluene, or xylene. The reaction i.s carried out in the presence of a tertiary organic base such as, for example, triethyl amine, or in the presence of an alkaline compound such as, for example, MgO or K2C03 in order to bind the hydrogen halide set free by salt formation. The reaction temperature is generally in the range of from 25 to 80C

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- 4 - HOE 78/F 258 When the reaction is terminated, the salt formed is fil-tered off or washed out with water and the amide I is iso-lated, optionally after removal of the organic solvent.
Method B) The phenoxy-phenoxy-propionic acid esters (III) are converted into the corresponding amides (I) by reaction with an excess amount of the respective amine IV, preferably in aquoeus solution at temperatures from 40 to 80C.
Method C) The direct reaction of V with VI is usual-ly carried out in one of the solvents specified sub A) and 10 in the presence of bases such as, for example, K2C03 or triethyl amine, to bind the hydrogen halide set free. Al-ternatively, phenolates obtained e.g. by reacting V with alkali can be used as starting materiaL. In this case, the reaction temperature is in the range of from 40C to the 15 boiling point of the solvent.
The starting compounds of the formulae II, III and V
are prepared by methods known from literature, for example as described in DE-OS 2,632,581.
The compounds I obtained as described above can be purified 20 by conventional methods, for example by recrystallization.
As compared with known compounds of similar structure (cf. DE-OS 2,632,581, US-PS 3,652,645), the compounds of the invention are iistinguished by a better herbicidal ac-tivity and selectivi'cy in crops. Particularly in the pre-25 emergence process they exhibit a good herbicidal effectagainst a number of mono- and dicotyledonous weeds which raise importar.t ecor.omical problems in various agricultu-ral regions. They control for example goose grass (Galium), 29 an important weed in European and American agricul tural ,, .
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- 5 - HOE 7~/F 258 areas, besides other types of weeds.
The compounds in accordance with the invention (I) are well tolerated by a great number of crop plants, for example cereals, rice, maize, soy bean, cotton, and rape.
In cultures of the said plants no or minor damages only are observed even with concentrations of 2.4 kg/hectare.
The novel compounds can therefore be used for the manufacture of herbicidal compositions containing from 2 to 95 % of the compounds as active substance. The composi-tions can be formulated as emulsifiable concentrates,wettable powders, sprayable solutions, dusts and granules, together with the usual additives.
~ ettable powders are formulations which are uniform-ly dispersible in water and which, in addition to the ac-tive compound and a diluent or inert material, also containwetting agents, for example, polyoxethylated alkylphenols, polyoxethylated fatty alcohols, alkylsulfonates or alkyl-phenylsulfonates and dispersing agents, for example sodium ligninsulfonate, sodium-2,2l-dinapthylmethane-6,6'-disul-fonate, sodium-dibutylnaphthalenesulfonate, or the sodium salt of oleoylmethyl taurine.
Emulsifiable concentrates are obtained by dissolving the active compound in an organic solvent, for example, butanol, cyclohexanone, dimethyl formamide, xylene or even higher boiling aromatics or hydrocarbons, and adding one or severa] emulsifiers, for example, calcium alkylarylsul-fonates such as calcium dodecylbenzene-sulfonate, or non ionic emulsifiers such as fatty acid polyglycol esters, 29 alkylaryl polyglycol ethers, fatty alcohol polyglycol ,-, , ~ 2~

- 6 - H~E 78/F 258 ethers, propylene oxide/ethylene oxide/ethylene oxide con-densation products, fatty alcohol/propylene oxide/ethyle-ne oxide condensation products, alkyl polyglycol ethers, sorbitan fatty acid esters, poyoxyethylene sorbitar. fatty acid esters or polyoxethylene sorbitol esters.
Dusts are obtained by grinding the active compound together with finely divided solid substances, for example talc, natural clays such as kaolin, bentonite, pyrophillite or diatomaceous earth.
Sprayable solutions, frequently commercialized as aero-sols, contain the active substance dissolved in an organic solvent and a suitable inert propellant.
Granules can be manufactured e:ther by spraying the active compound onto absorbent, granular inert material or by applying active compound concentrates by means of adhe-sives, for example polyvinyl alcohol, sodium polyacrylate or even mineral oils, onto the surfaces of carriers, such as sand, kaolinites or granular inert material. Suitable formulations can a]so be manufactured by 'che customary me-thods of manufacture of fertilizer granules, if desired inadmixture with fertilizers.
In the herbicidal compositions the conentrations of the active compounds in the commercial formulations may vary. In wettable powders, the active compound concentra-- 25 tion varies, for example, between about 10 and 80 %, the remainder consisting of the abovementioned formulation ad-ditives. in the case of emulsifiable concentrates, the ac-tive compound concentration is about 10 % to 80 %. Dust 29 formulations usually contain 5 - 20 % of active compound, "
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- 7 - ~OE 78/F 258 and sprayable solutions about 2 - 20 %. In the case of granules, the active compound content in par~ depends on whether the active compound is in a liquid or solid form and what granulation auxiliaries, fillers and the like are used.
The commerci.al concentrates are diluted prior to appli-cation in the usual manner, for example by means of water in the case of wettable powders and emulsifiable concentra-tes. Dusts, granules and sprayable solutions need not be diluted with further inert material prior to use. The amount of active ingredients necessary for obtaining the desired result depends on external conditions such as tem-perature, humidity and the like. It may vary within wide limits, for example between 0.1 and 10.0 kg Or active sub-stance per hectare, preferably however, between 0.3 and5 kg/hectare.
The active compounds according to the invention can be combined with other herbicides and soil insecticides.
According to another possible mode of application the active compounds according to the invention are mixed with fertilizers whereby compositions having a fertilizing and a herbicidal effect are obtained.
The following examples illustrate the invention.
EXAMPLES OF PREPARATION:

.
Method A~
0.1 mol of triethyl amine is added to 0.1 ~ol of an acid chloride (II) dissolved in 50 ml of toluene and 0.1 mol of an a~ine (IV) is added dropwise at 25 to 40C.
29 The toluene phase is separated, washed with water and . , . , . , ~ ............ .

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- 8 - HOE 78/F 258 dried over sodium sulfate. After distillation of the to-luene, the end product is isolated and purified by recry-stalliæation.
Method B) :
0.1 mol of phenoxy-phenoxy-propionic acid ester (III) is added at 40C to 0.2 mol of a 50 % aqueous amine solu-ti.on (IV). The mixture is stirred for 2 hours at 50C, fil~
tered off with suction, the precipitate is washed with wa-ter and the crystalline residue is dried.
The co~pounds prepared by the aforesaid rnethods are listed in the following table.

'~ ,~O~NO2 o (R1 )n O-CH-C-N~

Ex. (Rl)n R2 R3 ¦ m.p. L C_7 ¦ method (or nD) 2, 4-Cl H -(CH2)2 -OCH3 133-135 3 2 4-Br H -CH2 ~CH-CH2 . A
3 2, C1, 4-Br H -CH2 -CH-CHz . B
4 2 9 4-Br H -(CH2)2-C~;3 - A
2 5 4~Cl H -C ( C~3 )2 CN 160~161 A
6 2, 4~Cl H -CH2 -CH=CH2 125 127 A
~- 7 2,4-Cl H -(C~2 )2 ~OH oil A
8 2, 4-Cl H ~C (CH3 )2 -CH~ OH 105-108 3

9 2, 4-Cl H ~CH2 ~ 157-159 A
2, 4--Cl H -C (CH3 )2 ~) 113-116 A

., 3~

EX IR1) n R2 R3 ~-~-/ oc7 ¦ ~,ethod _~ ~
11 2-Cl, 4-~F3 H -CH2 -CH=CH2 123-126 A
12 2~-Cl,4-CF3 H -(CH2 )~-OCH3 102-105 B
13 2,4-Cl H _(CH2 )2-Sc~3 109~1'1 B
14 2,4-Cl H _(CH2 )3-SCH3 82 B
2, 4-C1 H - ( CH~ )3 -~ ( CH3 )~ 74- 77 B
16 2, 4-Cl CH3 -CH-C-CH 98-101 A
~ CH5 .
17 2,4-Cl CH3 -(CH2)2-CN oil A
18 2,4-Cl H -(CH2)3-OcH(cH3)2 84- 86 A J

19 2,4-Cl H CH ~ 167-170 A

2,4-Cl H ~ 165-16 8 A

21 2,4-Cl H ~

22 2,4-Cl -CH CH -O~CH CH -91 - 93 B
23 2,4-Cl -C~`~2CH2CH2CH2CH2 96 - 99 B
24 2,4-Cl -CH2CH2C~HCH2CH2113 -115 A

2,4-Cl 2 2 2 2 63 - 65 A
26 2-Cl,4-CF3 H ( 2)2 3 95 - 98 A
27 2-Cl~4-CF3 H -(CH2)3-N(CH3)281 - 83 A
28 2-Cl,4-CF3 H ~CH2)2 OH 98 -101 A
29 4-CF3 H -(CH2)2-OCH3 88 - 91 A
4-CF3 H -CH2-CH=CH2 128 -130 A
31 4-CF3 H ( ~)2 3 83 - 85 A
32 4-CF3 H -(CH2)3-N(C~13)2 63 - 65 A
33 4-CF3 H -~CH2)2-H 95 - 98 A

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- 10 - HOE 78/F 258 EXAMPLES OF FORMULATION
.
E X A M P L E A:
A wettable powder which is easily dispersible in wa-ter ls obtained by mixing 25 parts by weight of 2-/3-(2',4'-dichlorophenoxy)-6-nitro-phenoxy7~propionic acld methoxyethyl amide as ac-tive substance, 64 parts by weight of kaolin containing quartz as inert material, 10 parts by weight of potassium lignosulfonate and 1 part by weight of sodium oleoyl-methyl tauride as wet-ting and dispersing agent, and grinding the mixture in a pin mill.
E X A M P L E B:
A dust composition suitable for use as a herbicide is obtained by mixing 10 parts by weight of 2-/3-(2',4'-dichlorophenoxy)-6-nitro-phenoxy7-propionic acid methoxyethyl amide as ac-tive substance and 90 parts by weight of talc as inert material and grinding the mixture in a hammer mill.
E X A M P L E C:

.
An emulsifiable concentrate is obtained from 15 parts by weight of 2-/~-(2',4'-dichlorophenoxy)-6-nitro-phenoxy7-propionic acid methoxyethyl amide 75 parts by weig~t of cyclohexanone as solvent and 10 parts by weight of oxethylated nonyl phenol (10 EO) as emulsifier.

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~ HOE 78/F 258 E ~ A M P L E D:
A granular formulation consists, for exa~ple, of about 2 to 15 parts by weight of 2-~3-(2',4'-dichlorophenoxy)-6-nitrophenoxy7-propionic acid methoxyethyl amide and i.nert granular carrier material such as attapulgite, granular pumice and quartz sand.
BIOLOGICAL E AMPLES:
(Pre-emergence application) After sowing weeds in pots the compounds of the inven-tion were sprayed on the soil in the form of aqueous dis-persions of wettable powder concentrates. The plants were controlled as regards the herbicidal effect and the result was visually evaluated and expressed as percent of damage.
The results in Table I show that the substances ex-hi.bited very good herbicidal properties and kept well under control a great number of weeds.
Post-emergence application Various weeds were sown in pots and allowed to grow for about 3 weeks in a greenhouse to a height of 15 to 25 cm. The plants were then treated with the compounds ac-cording to the invention. The visual evaluation approxi- : -mately 4 weeks after application showed that the compounds according to the invention satisfactorily combated the weeds and that they were superior to the comparative com-pound Bifenox 5-(2,4-dichlorophenoxy)-2-n'~trobenzoic acid '.
methyl ester (cf. Table I).
Crop tolerance 29 Crop plants were sown in pots and treated prior to , " , . ~, , ,, : .. .:, , ~ -; . , ~ :
- . . . .

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- 1~ _ HOE 78/F 258 emergence with the compounds according to the invention.
The pots were kept under greenhouse conditions. The re-sults were evaluated 4 weeks after application Or the com-pounds and are listed in Table II. Even a high dosage of 2.4 kg of active substance (AS)/hectare did no or only little damage to the crop plants. The invention compounds are therefore useful for the selective control of weeds in crop cultures.

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Table Herbicidal activity against various weeds in percent ______________ .______________________________________________ pre-emergence application ~ Pa~lemceragtieonne ~Ex. Ikg AS/
No. ha S~I ¦ ~G A~iR i~T CRS MAT A~R CRS
---- _. ,............... _ .
6 2,4 100 65 100 90 75 _ _ 0,6 90 _ 100 _ _ _ _ 1 2,4 100 100 100 96 95 _ _ 0~6 100 95 100 95 85 _ _ _ 7 2,4 95 75 100 100 100 65 _ OD 6 85 _ 100 98 100 65 _

11 2S4 100 95 100 100 100 90 _

12 2,4 100 100 100 100 100 100 _ 0,6 100 100 100 100 100 100 _ 22 2,4 100 100 100 80 ._ _ _ 0,6 90 60 100 80 _ _ _ 8 204 75 75 100 90 75 _100 9 2,4 65 75 100 75 65 _ ~5

13 2~4 65 _ 100 98 85 90 95 80 0~6 35 _ 100 95 35 85 70 40

14 2,4 65 _ 100 _ 65 _ 8Q
2D4 ~ _ 100 75 _ _ 95 16 2~4 _ _ _ _ _ 100100 98 0~6 _ _ _ _ _ 95100 80 18 2,4 100 85100 100100 98100 100 2,4 _ _ _ _ .~ 95100 98 006 _ _ _ _ _ 90100 80 23 2~4 _ _100 _ _ 100100 100 0,6 _ _ 95 _ _ 8598 60 ,4 294 _ _100 _ _ 95100 98 0~6 _ _ _ _ _ 80100 80 204 98 ~100 90 85 95100 100 0~6 65 _100 35 35 90100 80 26 2,4 100 98100 100100 100100 100 0~6 100 60100 100100 100100 100 27 2~4 100 90100 100100 100100 100 0 ~6 98 20100 100100 100100 100 28 2,4 100 100100 100100 100100 100 0a6 100 100¦ 100 100100 100100 100 , .

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~ 14 - HOE 78/F 258 Ex kg ha/ SAL ECG A~IR l.~T CRS ~T A~l~ CRS
. _ _ .. _ . .
29 2~4100 100 100 100 80 _ _ 006100 100 100 100 60 _ _ 2~4100 95 100 _ _90100 95 0~6100 50 100 _ _7C 98 70 31 2~4100 80 100 100 90 _ _ 32 2 4695 30 100 80 40 _ _ 0~6 ~ _ 100 _ _ _ _ 33 2~4100 100 100 100 98 _ _ 0,6100 98 100 100 98 _ _ Compara-tlve agent (Bifenox) 0,665 50 95 100 35 0 _ SAL = Setaria ECG = Echinochloa AMR = Amaranthus MAT = Matricaria CRS = Chrysanthemum . .

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Claims (7)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. Phenoxy-phenoxy-propionic acid amides of the formula I
(I) in which R1 is halogen and/or CF3;
n is 1 or 2, R2 is hydrogen or (C1-C4)alkyl;
R3 is (C3-C6)alkenyl, (C3-C6)alkinyl, hydroxy-(C1-C4)-alkyl, (C1-C4)alkoxy-(C1-C4)alkyl, di-(C1-C4)alkyl-amino-(C1-C4)alkyl, cyano-(C1-C4)alkyl, (C1-C4)al-kylthio-(C1-C4)alkyl, (C5-C6)cycloalkyl, methyl-cyclohexyl, phenyl-(C1-C4)alkyl, pyridyl or pyri-midyl;
or R2 and R3 together form a 4 to 7-membered ring in which up to 2 carbon atoms can be replaced by N and/or 0.

2. Process for the manufacture of a compound of the formula I as claimed in claim 1, which comprises reacting (a) a phenoxy-phenoxy-propionic aeid halide of the formula (II) or a phenoxy-phenoxy-propionic acid ester of the formula (III) in which R is (C1-C8)alkyl, with an amine of the formula (IV) or (b) reacting a 3-hydroxy-4-nitro-diphenyl ether of the formula (V) or a corresponding phenolate with a halo-propionic acid amide of the formula (VI) in which Hal is chlorine or bromane, optionally in the presence of acid-binding agents.

3. Method of combating weeds which comprises applying to the locus of weed growth an effective amount of a compound as claimed in claim 1.

4. 2-[3-(2',4'-Dichlorophenoxy)-6-nitrophenoxy]-propionic acid hydroxy-ethyl amide.

5. 2-[3-(2'-Chloro-4'-trifluoromethyl)-6-nitrophenoxy]-propionic acid methoxyethyl amide.

6. 2-[3-(2'-Chloro-4'-trifluoromethyl)-6-nitrophenoxy]-propionic acid methylthioethyl amide.

7. 2-[3-(2'-Chloro-4'-trifluoromethyl)-6-nitrophenoxy]-propionic acid hydroxyethyl amide.