DE2229062A1 - N-ALKYL-ALPHA-PHENOXYALKYLAMIDES AND THEIR USE AS HERBICIDES - Google Patents

Description

LAWYERS,

DR. JUR. DIPL-CHEM. WALTER BEIL U, June 1972

ALFRSO HQi] PPENER

DR. JUR. Tue * .- CHtM. H.-J. WOLFF

BR. JUR. HOUSE CMR. AX

623 FRANKFURTAM MAIN-HOCHST

AOetONSrBASS £ 58

Our no. 17 868

Stauffer Chemical Company New York, N.Y., V, St.A.

N-alkyl-a-phenoxyalkylamides and their use as herbicides

The present invention relates to new N-alkyl-a-phenoxyalkylamides, which are substituted in the 3,5-position of the phenoxy group, as well as the use of these compounds as Herbicides.

The compounds according to the invention are new substances and correspond to the formula

HIGH
llll ι.
0-C-ON-R

1 2
Ln where R and R are each a halogen atom, preferably a chlorine atom, or an alkyl radical with 1 to 4 carbon

atoms, preferably a methyl radical, R an alkyl radical with 1 to 4 carbon atoms, preferably an ethyl f'i '-. i, and R oinen alkyl radical with 1 to 7 carbon atoms In. "!

2 ° ^{9882 / m1}

In the above discussion of the compounds of the invention, the alkyl radicals include both straight-chain and branched-chain configurations, e.g. B. methyl, ethyl, n-propyl-j isopropyl, n-butyl, sec-butyl or tert-butyl radicals. The term "halogen atom ¹¹ includes chlorine, bromine, iodine and fluorine atoms.

The closest prior art is:

1. DOS 1 943 289

2. J. Sudi et al., Journal of Experimental Botany, Vol. 12, pp. 390-400 (1961), (CA 56 ^ 14661c)

3. Novenyved. Tud. Tanacskozas Kozlernen., (Budapest), Volume 2, pp. 401-411 (I960), (CA ^ 7 14224c)

4. J. Sudi et al, Botanical Gazette (Chicago), Vol. 123, pp. 265-272 (1962), (CA 52 7639h).

The compounds of the invention are active herbicides of a general nature; H. they are across from a wide area of plant varieties effective as herbicides. According to the method according to the invention for combating undesirable Vegetation will provide a herbicidally effective amount Compounds described applied where a fight is desirable.

The term "herbicide" used here is understood to mean o a compound with which the vegetation fight each other odor can be modified. By "a plant growth controlling amount" is meant the amount of the compound which has a modifying effect on plant growth. Such modifying effects include all deviations from natural development, e.g. B. Destruction, growth retardation, defoliation, desiccation, Regulation, growth therapy, root treatment, stimulation

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or stunting. "Plants" are germinating seeds, emerging seedlings and existing vegetation, including roots and aboveground parts.

The compounds of the invention are made according to the following general procedure made:

Level a

H 0
Il

- / - OH + BrC-C-OH + NaOH

-C-C-OH +

NaBr

Generally one mole of the phenol becomes a minor molar Excess of the α-bromoalkanoic acid and about 3 moles of sodium hydroxide mixed in water at about 10-15 ° C. The reaction mixture is then refluxed for about 2 hours. The mixture is then cooled and diluted with water. The pH of the mixture is adjusted with 19% hydrochloric acid set to 8. The solution is extracted several times with ether, and then the pH is adjusted to 19% HCl adjusted to 2. An oil separates out, which is extracted with ether.

After drying and evaporation of the ether, the desired Product obtained in the form of a solid. The solid is purified by recrystallization from cyclohexane.

2 09882/12 41

Level B *

HO O

I H II

O-C-C-OH + Cl-C-Cl

HO
OCC-Cl + HCl

First, the acid is mixed with benzene. Then a small amount of dimethylformamide is added and the slurry is heated. A slight excess of phosgene is then added in portions to the acid mixture. The reaction is after the evolution of HCl has ceased closed. By evaporating the reaction mixture, the desired product is obtained in the form of a liquid.

Level C V. H O J OH
Il I R ¹ . R ^c -OCCNR ⁴
I q
R ^ö R ² i H
I. Rl R ² -

Approximately equimolar amounts of the amines are dissolved in benzene. The solution is cooled to about 10 ⁰ C. The acid chloride dissolved in benzene is added to the amine solution so slowly that the temperature is kept between 10-15 ° C. The reaction mixture is warmed to room temperature until the reaction is complete.

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The reaction product is then diluted with ELO and poured into a separatory funnel. The aqueous layer is separated and discarded. The organic phase is washed twice with 10% HCl and twice with 5% Na ₂ CO _3. After drying, the organic layer is first evaporated on a water jet pump and then on an oil pump, the desired product being obtained.

The preparation of the compounds according to the invention is carried out by the example below explains.

example N-isopropyl-a- (3,5-dichlorophenoxy) butyramide

100.0 g (0.614 mol) of 3,5-dichlorophenol and 112.5 g (0.675 mol) of α-bromobutyric acid were mixed, and then 100 ml of water was added. The mixture was cooled in an ice water bath to 10 ° C and at about 10-15 ⁰ C with 14 to 7.2 g (1.842 mol) of 50% NaOH was added dropwise. The reaction mixture was warmed to room temperature and then refluxed for two hours?: +. After the mixture was cooled, it was diluted to 600 ml with H0 and the pH was adjusted to 8 with 19% HCl. The aqueous solution was extracted three times with portions of 150 ml of ether and then adjusted to pH 2 with 11% HCl. It separated out a Ö "l from, which was extracted with ether After drying and evaporation dos ether remained 94.3 g of a white solid having a melting point of 102 -... I08 ⁰ C back wurdo This solid ana 2 50 ml of cyclohexane umkrirstallisiert , 71.8 g of a- (3,5-D.ichlorphenoxy) -but!: orric acid with a melting point of 11-116 ° C were obtained.

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71.8 g (0.288 nox) a- (S, 5-dichlorophenoxy) butyric acid and 75 ml of benzene were placed in a 500 ml flask fitted with a dropping funnel with a dry ice condenser. The slurry was stirred and 0.2 ml of dimethylformamide was added. The mixture was ^{heated to 35 °} C. and 10 g of phosgene were condensed into the mixture to initiate the reaction. The start of the reaction was indicated by evolution of HCl and foaming. A further 26.0 g of phosgene were added in portions of 5 g. After the reaction had ended (evolution of HCl had ended), the reaction mixture was evaporated to give 77.6 g of α- (3,5-dichlorophenoxy) butyryl chloride

20 remained in the form of a liquid residue, n _n = 1.5345.

2.8 g (0.046 mol) isopropylamine and 5.1 g (0.050 mol) triethylamine were dissolved in 60 ml benzene, and the solution was cooled ^{to 10 ° C. in an ice-water bath.}

10.0 g (0.044 mol) of a- (3,5-dichlorophenoxy) butyryl chloride were dissolved in 40 ml of benzene, and the solution was added so slowly that the temperature of the reaction mixture remained between 10 and 15 ^° C. After completion of the addition, the reaction mixture was warmed to 2 8 ⁰ C; the heating mantle was then removed and the reaction mixture allowed to return to room temperature. The equipment was left standing over the weekend. The reaction product was then diluted with 250 ml of H0 and poured into a funnel. The aqueous layer was separated and discarded. The organic phase was washed twice with 250 ml of 10% i> ev HCl and twice with 250 ml of 5% Na ₂ CO _3. After drying, the organic layer was first evaporated on a water jet pump and then on an oil pump, 9.8 g of a solid with a melting point of 80.5-8 3.5 ^° C. remaining.

The table below shows some selected compounds compiled, which can be produced by the method described above. The connections assigned numbers have been given in the broad description maintained.

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Table I.

= x HOH

I I ι

0-C-C-N-R

link
No. R ¹ R ² R ³ R ⁴ 1 -CH ₃ -CH ₃ -CH ₂ CH ₃ -CH (CHg) ₂ 2
3 -CH ₃
-CH ₃ -CH ₃
-CH ₃ -CH ₂ CH ₃
-CH ₂ CH ₃ -CH ₀ CH ₂ CHg
-CH (CH ₃ ) CH ₂ CH ₃ 4th -CH ₃ -CH ₃ -CH ₂ CH ₃ -CH ₂ CH ₂ CH ₂ CHg 5 -CH ₃ -CH ₃ -CH ₂ CH ₃ -CH ₂ CH (CHg) CHg 6th -CH ₃ -CH ₃ -CH ₂ CHg -CH ₃ 7th -CH ₃ -CH ₃ -CH ₂ CHg -CH ₂ CHg 8th Cl Cl -CH ₂ CH ₃ -CH (CHg) C (CHg) ₃ 9 Cl Cl -CH ₂ CH ₃ -CH (CHg) CHg 10 Cl Cl -CH ₂ CH ₃ -CH ₂ CH (CHg) ₂ 11 Cl Cl -CH ₂ CH ₃ -CH (CHo) CHoCHo 12 ■: ■ ' Cl Cl -CH ₂ CH ₃ -CH ₃ 13th Cl Cl - CH _n / CHq -CH ₂ CH ₃ 14th Cl Cl —CH ο CH ο -CH (CH ₂ CHg) ₂ 15th Cl Cl -CH ₂ CHg -CH (CHg) (CH ₂ CH ₂ CHg) 16 Cl Cl -CH ₂ CHg -CH (CHg) CH (CHg) CH ₂ C 17th Cl Cl -CH ₂ CHg, - C (CHο) ., CH., Ci PH. ) -j 18th Cl Cl -CH ₀ CHq -C (CHg) ₃ 19th CH ₃ CH ₃ -CH CH ₃ -C (CHg) ₃

Testing of herbicidal effectiveness

As already mentioned, the connections according to the invention are phytotoxic compounds that are suitable for combating various types of plants. The compounds according to the invention were tested as herbicides in the following manner.

according to
at the

2Q9882 / 12A1

Testing as pre-emergence herbicides

The day before the treatment, seeds from seven different types of weeds were sown in individual rows, one type being used per row across the width of the box. The seeds used were Digitaria sanguinalis (L.) Scop., Setaria glauca (L.) Beauv., Echinochloa crüsgalli (L.) Boauv., Avena sativa (L.), Amaranthus retroflexus (L.), B rassica junce a (L.) .) Coss. and Rumex crispus (L.) related. Depending on the size of the plants, these seeds were sown in such a way that after emergence there were about 20 to 50 seedlings in a row. After sowing, the boxes were watered. To prepare the spray solution, 50 mg of the test compound was dissolved in 3 ml of a solvent, e.g. B. acetone, with a content of 1% Polyoxyäthylensor> bitanmonolaurat (Tween 20) dissolved. The next day, each box was sprayed with the spray solution in the proportion of 2.24 g of the test compound per

3 2

75 cm of the solution is sprayed per m. An atomizer was used to spray the solution onto the soil surface. The boxes were placed in a greenhouse at a temperature of 26.7 ° C and watered regularly. Two weeks later the degree of weed killing was determined, with the germination and growth of each weed species in the treated boxes with that of the same weed species in different untreated ones Kon-crol! Boxes was compared. The rating system was the following:

= no noticeable damage (0 - 15% destruction)

+ = slight damage (25 - 35% destruction) + + = moderate damage (55 - 6 5% destruction) + + + = serious damage or destruction (85 - 100% destruction)

To the overall effectiveness with all seven weeds · clay to an efficacy index was used. He is· the sum of the number of plus signs so that an effectiveness is ex of 21 the almost complete annihilation of all

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Means 7 types of weeds. The results of this test will be shown in Table II.

Testing as post-emergence herbicides

The seeds of the δ weed species Digitaria sanguinalis, Echinochloa crusgalli, Avena sativa, Brassica juncea and Runaex crispus and a culture of pinto beans (Phaseolus vulgaris) were planted in boxes as described above for the pre-emergence herbicide test. The boxes were at a temperature of 22.2 - uaci found 29, M ⁰ C in the greenhouse THP-lich irrigated with a sprinkler. About 10 to 1 minute after planting, when the cotyledons of the bean plants had almost completely unfolded and the first diurnal leaves were just about to form, the plants were sprayed. To prepare the spray preparation, 50 mg of the test compound were weighed out, dissolved in 5 ml of acetone containing 1% polyoxyethylene sorbitan monolaurate, and then 5 ml of water were added. The solution was sprayed onto the leaves using an atomizer. The concentration of the spray preparation

2 crug 0.5% and the amount applied would be about 2.2H g / m 2 if all of the spray was left on the plant and on the ground, but some of it works dom spray preparation lost, so the amount applied

is estimated to be around 1.4 g / m.

The beans were used to defoliate and to detect plant growth regulators. The beans were reduced to 2 or 3 plants per box, being the excess weaker plants a few days before were cut off after treatment. The treated plants were placed back in the greenhouse, whereby one strictly ensured that the treated foliage was sprayed with water for up to 3 days after treatment was avoided. The water was fed to the ground in a slow stream of water from a water hose, whereby care was taken not to get the foliage wet.

2 0 9 8 8 2/1241 bad ORiGiNAL

Damage ratings were recorded 14 days after treatment. It was the same rating system as used for the pre-emergence test, where C-), (+), (++) and (++ ι ·) for the different degrees of damage and the Annihilation were used. The damage symptoms were also registered. The maximum impact index for the total destruction of all types of post-emergence herbicide test is 18, where this number means the sum of all plus signs used with the 6 in this experiment Plant varieties were obtained. The herbicidal effectiveness is given in Table II.

Table II the exam on Pre-emergence herbicidal effectiveness Results Herbicide Effectiveness Index ' (2.24 g / m ² link 21 Sewing up No. 21 ) (1.4 g / m ² ) 1 20th 16 2 21 17th 3 21 10 4th 21 15th 5 21 16 6th 13th 17th 7th 20th 16 8th 21 11 9 19th 14th 10 20th 15th 11 21 14th 12th 6th 14th 13th 15th 16 14th O 2 15th 0 11 16 20th 5 i 17 21 5 18th 15th 19th 9

2Q8882 / 1241

21 = 85 - 100% destruction of all 7 plant varieties tested before emergence

18 = 85 - 100% destruction of all 6 plant varieties tested after emergence

The compounds according to the invention are used as pre- or post-emergence herbicides and are applied in different ways and in different concentrations. In practice, the compounds according to the invention are processed into herbicidal compositions by mixing them in herbicidally effective amounts with extenders and carriers such as are customarily used to facilitate the dispersion of the active ingredients for agricultural purposes. It should of course be noted that the type of preparation and the type of application of the preparation can influence the action of the materials as herbicide. Thus, depending on the desired type of application, the effective herbicidal compounds can be converted into relatively coarse-grained granules, wettable powders emulsifiable concentration). su powdery dusts, solutions and various other known types of preparations. Preferred formulations for herbicides which are used as pre- or post-emergence herbicides are wettable powders, emalgatable concentrates and granules. These preparations can contain amounts of as little as about 0.5 up to about 95% or more of active ingredient. The amount to be applied depends on the type of seeds or plants to be controlled _: and the

2 2

Bring ratio is between 0.112 g / m and 5.6 g / m

Wettable powders are in the form of finely divided lights that can easily be dispersed in water or another dispersant. The wettable powder is finally applied to the soil either as dry dust or as a dispersion in water or other liquid. Typical carriers for wettable powders are, for example, Fuller's earth. Kaolin clays, silica and other easily wettable organic or inorganic extenders. 1! "etchable ·; ^1. Powders are usually manufactured in such a way that they

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about 5 to about 95% of the active ingredient and generally also a small amount of a wetting, dispersing or emulsifying agent included, which facilitates wetting and dispersing.

The emulsifiable concentrates are homogeneous liquid preparations that are placed in water or another Dispersants are dispersible; they can consist entirely of the active ingredient mixed with a liquid or solid Emulsifiers consist; but they can also use a liquid carrier such as xylene, heavy aromatic petroleum hydrocarbons, Contain isophorone or other non-volatile organic solvents. For use as herbicides these concentrates are dispersed in water or another liquid carrier and usually on sprayed onto the area to be treated. The percentage by weight of the active ingredient can vary depending on the type of Aufbrinuung of the agent may be different, but is generally, based on the herbicidal agent, from about 0.5 to 95% active ingredient.

Granules in which the toxic agent is carried on relatively coarse particles are generally used applied without dilution to the area to be freed from weeds. Typical carriers for granulates are sand, Fuller's earth, bentonite, vermiculite, perlite and others organic and inorganic materials that absorb or coat the toxic agent can be. Granules are generally prepared so that they contain about 5 to about 25% active ingredient; they can also contain small amounts of other ingredients, e.g. B. surface-active agents such as butchering agents, Dispersants or emulsifiers, oils, e.g. B. heavy aromatic petroleum hydrocarbons, kerosene or other petroleum fractions or vegetable oils and / or adhesives such as dextrins, glue or synthetic resins.

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Typical wetting, dispersing or emulsifying agents used for agricultural preparations are, for example, alkyl and alkylarylsulfonates and. -auirates as well as their sodium oils, menstrual alcohols, as well as other types of surfactants, many of which are commercially available. When a surfactant is used, it is usually in amounts of 0.1 to 15 weight percent in the hurbicidal agent available.

Dusts that are flowable mixtures of the ' • ■ / active ingredient with foin-distributed solids such as talc, clays, M '.'. Hien and other organic and inorganic solids, di · ;; as a dispersant and carrier for the toxic Center; L serve, acts, are suitable when the preparations are to be introduced into the ground.

Pastes, which are homogeneous suspensions of a finely divided solid toxic agent in a liquid carrier, e.g. B. water or oil, is whoever uses <Wi for special purposes. This Präpaivite contain the active ingredient in amounts of about 5 to 9 5 parts by weight ^o o; in addition, they can be low. Contain quantities of a wetting, dispersing or emulsifying agent to facilitate dispersion. The pastes are used for application. iclw.; i.-wpi f. pre-thinned and sprayed onto the area to be treated.

vi.-iitorci, preparations which can be used for weed control are z. Usually simple solutions of the active ingredient in a dispersant in which it is completely soluble in the desired concentration, such as. B. acetone, alkylated Naphtli'ilino, xylene or other organic solvents. Spray solutions under pressure, e.g. B. aerosols _s in drug deien by evaporation of the used as the carrier, the low-boiling solvent, eg. B. Freons, dispersed in a variable form, can also be used.

The phytotoxic agents of the present invention are applied to the plants in a conventional manner. So the dust and liquid means by means of mechanical Spray sprayers, boom sprayers, hand sprayers, and spray atomizers onto the plant. The funds can also be in the form of dust or Sprühnebol -ms aircraft, as they are very low Dosages are effective. For example, to modify the growth of germinating seeds or emerging seedlings To fight ou'ir, dust and liquid become means using conventional methods on the. Applied to the soil and distributed in the soil to a depth of at least 1.2 7 cm below the surface of the earth. Phytotoxic agents but do not need to be mixed with the soil particles, as these agents can also be sprayed or sprinkled on the soil surface can be applied. The inventions phytotoxic agents can also be applied by adding them to the water used for irrigation treated soil is used. This method allows the agent to penetrate the soil when the water is off the bottom is absorbed. Leave dust preparations, granules or liquid preparations that are applied to the soil surface using conventional methods, e.g. B. plowing, harrowing or mixing processes, distribute under the soil surface.

The phytotoxic agents of the present invention can also contain other additives, e.g. B. fertilizers, pesticides and the like., as an aid or in combination with any of the above mentioned tools are used. Furthermore, in combination with the inventive Compounds other phytotoxic compounds, e.g. B. 2, ^ - dichlorophenoxyacetic acids, 2,4,5-trichlorophenoxyacetic acid, 2-methyl-4-chlorophenoxyacetic acid and its salts, esters and amides, triazine derivatives, such as 2,4-bis (3-methoxyprouylamino) -6-methylthio-s-triazine, 2-chloro-4-ethylumino-6-isopropylamino-s-triazine and 2-ethylamino-4-isopropylamino-6-mathylmercapto-s-triazine, Urea derivatives, such as 3- (3,4-di- "lilophenyl) -l, l-dimethy ! urea and} - (p-chlorophenyl) -l, 1-

209882/1241

dime thy lurea, acetamides, such as N, N-diallyl-a-chloroacetamide and the like, benzoic acids such as 3-amino-2,5-dichlorobenzoic acid, Thiocarbamates, such as S-propyl dipropyl thiocarbamate, S-ethyl dipropyl thiocarbamate, S-ethyl cyclohexyl ethyl thiocarbamate, S-ethylhexahydro-lH-azepine-l-carbothioate and the like., 4- (Methy! Sulfonyl) -2,6-dinitro-N, N-substit.-aniline, such as 4- (methylsulfonyl) -2, 6-dinitro-N, N-di-n-propylaniline, M - trifluoromethyl-2,6-dinitro-N, N-substit.-aniline, such as 4-trifluoromethyl-2,6-dinitro-NjN-di-n-propylaniline and H-trifluoromethyl-2,6-dinitro-N-ethyl-N-n-butylaniline.

Fertilizers in combination with the invention active agents can be used, are z. B. ammonium nitrate, Urea and superphosphate. Other valuable additives ^ 3ind z. B. Materials in which plants take root U'.id can grow, such as compost, humus, sand and the like.

The concentration of a compound of the invention that an effective amount in the best form of application at the The use disclosed herein is easily determined by one skilled in the art.

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Claims (1)

- 16 - Claims
1. N-alkyl-a-phenoxyalkylamides of the formula HIGH
ι «ι 0-C-ON-R
ι ο 1 2
where R and R are each a halogen atom <Mer an alkyl radical with 1 to 4 carbon atoms, R an alkyl v ^ .qf- with 1 to H carbon atoms and R an alkyl radical with 1 to 7 carbon atoms. 2. A compound according to claim 1, characterized in that 12 3 R and R of the formula in each case a chlorine atom, R an ai.iiyi-i «··. · + - and r ' ¹ the radical -CH (CH ₃ ) (CH ₂ CH ₂ CH ₃ ). 3. A compound according to claim 1, characterized in that 12 3 R and R of the formula each represent a methyl radical, R represents a Ethyl radical and R is an isopropyl radical. M-. Connection according to claim 1, characterized in that 12 3 R and R of the formula each a chlorine atom, R an ethyl rest and R represent an ethyl radical. 5. A compound according to claim 1, characterized in that 12 3 R and R of the formula each a chlorine atom, R an ethyl rest and R is a tert-butyl radical. 6. A compound according to claim 1, characterized in that 12 3. R and R 'of the formula each represent a methyl radical, R an ethyl H
rest and R is a tert-butyl radical. 209882/1 2 Λ 1 7. A compound according to claim 1, characterized in that 12 3 ? - and R of the formula each represent a methyl radical, R a methyl radical and R a tert-butyl radical. 8. A method for combating unwanted vegetation, characterized in that an area in which the control of vegetation is desired, a growth-combating amount of viifios N-alkyl Ί- phenoxy alky lamids according to any one of claims 1 to 7 is applied. For Stauffer Chemical Company New York, N.Y., V.St.A. (Dr H.J. Wolff) Lawyer 209882/1241 BAD ORiQsNAL