DE3038083A1 - 5- (2'-CHLOR-4'-TRIFLUORMETHYLPHENOXY) -2-NITROSTYROL DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND HERBICIDES CONTAINING THESE COMPOUNDS - Google Patents

Description

description

In'der JP-PS 135 220/75 herbicidal 5- (2,4-dichlorophynoxy) -2-nitrocinnamate ester described.

US Pat. No. 4,046,798 to 3,928,416 describes herbicides 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoate ester.

U.S. Patent 4,063,92-9 has herbicidal salts of 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoic acid Go to content.

The present invention relates to new herbicidal compounds, compositions containing them and methods of their use. The invention is based on the finding that certain substituted 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrostyrenes have herbicidal activity. In particular, compounds of the formula (I.)

CH = CHR

where R is carboxy, carboalkoxy, carbamoyl, halogen, cyano, Carboalkylthio, thiocarbamoyl, alkylcarbonyl, alkylcarbonyl, substituted halogen or alkoxy, alkylthio, nitro or amino, herbicidally active. The agents according to the invention are suitable for both pre-emergence and post-emergence uses, with a selective herbicidal activity against broad-flowered plants.

The compounds according to the invention correspond to the formula (I)

130037/0604

ORIGINAL INSPECTED

■ Γ ---

CH = CHR

where R has the following meanings:

"11

-CR, where R is hydroxy, alkoxy with 1 to 4 carbon atoms, optionally substituted by halogen or alkoxy with 1 to 4 carbon atoms, alkyl with 1 to 4 carbon atoms, optionally substituted by halogen or alkoxy with 1 to 4 carbon atoms, Aralkoxy with 6 to 8 carbon atoms, amino, optionally substituted by 1 or 2 alkyl groups with 1 bii 4 carbon atoms, or aralkyl with 6 to 8 carbon atoms,

"- + +
-CO M, where M is a metal or organic cation, such as sodium, potassium, ammonium or tetraalkylammonium, '

-CR, where R is amino, optionally substituted by 1 to 2 alkyl groups with 1 to 4 carbon atoms,

"33 '

-CSR, where R is aralkyl of 6 to 8 carbon atoms or alkyl of 1 to 4 carbon atoms, optionally substituted by calogen or alkoxy with 1 to 4 carbon atoms, means,

-OR, -SR, nitro, halogen, amino, optionally substituted by 1 or 2 alkyl groups with 1 to 4 carbon atoms .

Representative examples of the groups R are carboxy, Carbomethoxy, carboethoxy, carbobenzoxy, N, N-dimethylcarbainoyl, NjN-diethylcarbamoyl, sodium carboxylate, potassium carboxylate, Tetramethylammonium carboxylate, bromine, fluorine, chlorine, iodine, cyano, carboethylthio, Ν, Ν-diethylthiocarbainoyl,

130037/0604

Methylcarbonyl, ethylcarbonyl, 2-methoxycarboethoxy, Methoxy, ethoxy, methylthio, ethylthio, nitro, methylafnino, Dimethylamino. or diethylamino.

Preferably R is carboalkoxy. In particular, R is carbomethoxy or carboethoxy.

The compounds of the present invention in which R is carboalkoxy / can according to the following reaction scheme getting produced:

HO

(Ila)

IHa

(IV)

(II)

CH = CHCO ₂ H

CH = CHCO ₂ -K ^{+ KC1}

(3)

CH = CHCOR ¹

+ SO ₃ H (OCH ₃ )

iv

H ₂ SO

CH = CHCOR ¹

130037/0604

The reaction (1) can be carried out under conventional condensation reaction conditions. The reaction is generally carried out at temperatures from 60 to 150 ^° C. in the presence of a base, such as pyridine, in an inert organic solvent. Suitable solvents are benzene, toluene and xylene.

Reaction (2) can be carried out in such a way that the potassium disalt of phenol (Ha) is first prepared and the disalt with Äcjuimolararen. Quantities of 1, 2-dichloro-4-trifluoromethylbenzene at 140 to 170 ⁰ C in a solvent such as diraethyl sulfoxide, in the presence of a mild base such as potassium carbonate, is reacted. The product (III) is generally purified by conventional methods, for example by extractone, distillation or crystallization.

Reaction (3) is prepared by reacting equimolar amounts of the acid (purple) with an alkylating agent such as dialkyl sulfate in an inert solvent such as acetone. The reaction is exothermic and is maintained by cooling to 0 to 20 ⁰ C. The product (IV) is isolated by conventional methods.

The reaction (4) is carried out according to conventional nitration methods, namely by treating the ester (IV) under nitration conditions in an inert solvent such as dichloromethane, ie by treating with a nitrating agent such as concentrated sulfuric acid and concentrated nitric acid at 0 ^° C. Product (V) can be isolated using conventional methods.

The compounds according to the invention in which R is halogen can be made as follows:

ORIGINAL INSPECTED

130037708D4

HIa + χ.

- ft -

(X = balogen)

■ egg

(VII)

CH = CHX

Cl

(VIII)

CH = CHX

Reaction (5) is a conventional halogen addition, while reaction (7) is a conventional one Nitration, which is similar to reaction (4). The reaction (6) can be carried out by stirring a base such as Potassium carbonate, with the acid 4VI) in a suitable Solvents such as acetone can be carried out at room temperature. The reaction is usually after 2 to Completed 12 hours.

The compounds of the formula I in which R is alkylthio, cyano, nitro, amino or alkoxy can be prepared by treating the halogenotyrene compound VIII, where X is preferably Br, with a suitable nucleophilic compound. The compound in which R is -CNR ¹ R "can be obtained by converting the acid

■ I

(purple) into an amide followed by treatment with P ₂ ^ c to convert the carbamyl group to a thiocarbamyl group and nitration according to the reaction (4). The compounds of formula I in which R is for

130037 / 060A

-CR ¹ can be treated according to standard methods

of the salt (III) can be prepared with a reagent such as R ^{1 Li.}

The compounds of the invention are generally Herbicides that are suitable for both pre-emergence and post-emergence application. To carry out a Vorauf control of unwanted vegetation the herbicidal compounds in herbicidally effective amounts on the site or growth medium of the vegetation applied, for example on soil that is infected with seeds and / or seedlings of such vegetation. This application inhibits or kills the growth of the seed, the germinating seed or the seedlings. For post-emergence purposes, the herbicidal compounds are applied directly to the leaves or other parts of the plant upset. In general, the herbicidal compounds according to the invention are particularly effective against broad-leaved weeds. Some are selective as to the type of application and / or the type of weed.

If the compounds are applied to growing plants above the ground in such an amount that the Compounds do not kill crops, then an effective plant growth regulating or inhibiting one will also be effective Effect found so that these compounds in an advantageous manner, for example to prevent or Delaying the growth of side buds of plants, as well as eliminating superfluous fruits in different fruit trees can be used.

The compounds can be used in a variety of means. In general, the compounds be stretched with a known carrier material, both

130037 / Q6JU ORlQiNAL INSPECTBD

for example with inert solids, water and organic Liquids.

The compounds are the means in such a Amount added sufficient to exert a herbicidal or growth-controlling effect. Usually approximately 0.5 to 95% by weight of the compounds are used in such formulations.

Solid agents can be made using inert powders. The means can be homogeneous Acting powders that can be used as such, also being diluted with inert solids under Formation of dust is possible. It can also be suspended in a suitable liquid medium for spraying purposes take place. The powders usually consist of the active ingredient with minor amounts of a conditioning agent is mixed. Natural = clays, either absorptive, such as attapulgite, or relatively non-absorptive, such as kaolins, diatomaceous earth, synthetic finely divided silica, calcium silicate or other solid inert Carriers conventionally used in powdered herbicidal compositions can be used will. The active ingredient usually makes up about 0.5 to 90% of these powdered compositions. The solids should normally be very fine-grained. For a conversion of the powder into dusts are in conventional Way talc, pyrophyllite or the like. Used.

Liquid preparations which contain the active ingredients described above can be prepared by mixing the respective compound can be prepared smedium with a suitable liquid dilution medium. Typical liquid media, which are conventionally used are methanol, benzene, toluene and the like. The active ingredient makes usually about 0.5 to 50% of these liquid formulations. Some of these preparations can be used as such used while others with large amounts

130 037/0 60 4

ORIGINAL INSPEGTBD

be stretched.

Preparations in the form of liquid powders or liquids may contain one or more surfactants, such as wetting agents, dispersants or emulsifiers. The surfactants cause Preparations made from wettable powders or liquids are easily dispersed or emulsified in water, whereby aqueous sprays can be obtained.

The surfactants used can be anionic, cationic or nonionic for example long-chain sodium carboxylates, alkylarylsulfonates, Sodium lauryl sulfate, polyethylene oxides, lignosulfonates and other surfactants.

For use to carry out a pre-emergence treatment, it is expedient to use a fertilizer, an insecticide, add a fungicide or other herbicide.

The amount of active compound or agent used varies depending on the particular one to be contacted Part of the plant or the plant growth medium and the place of use, d. H. of whether it is shielded environments such as greenhouses as opposed to exposed areas such as fields. Further the amount depends on the degree of control desired. In general, both in the case of a Pre-emergence and post-emergence weed control the compounds according to the invention in amounts of 0.2 to 60 kg / ha used, the preferred amount being between 0.5 and 40 kg / ha. For a plant growth regulator or inhibiting effect, it is essential to use the oxo compounds in a concentration which is not so high that the plants are killed.

ORIGINAL INSPECTED

130Ö37 / 06G4

Therefore, the amounts used are to achieve a plant growth regulating or plant growth inhibiting Activity generally lower than the amounts used to kill plants. Generally these amounts vary from 0/1 to 5 kg / ha and preferably 0.1 to 3 kg / ha.

Herbicidal tests using representative tests according to the invention Connections are carried out according to the following methods:

Herbicidal pre-emergence test

An acetone solution of the test compound is prepared by mixing 375 mg of the compound, 118 mg of a nonionic surfactant and 18 ml of acetone. 10 ml of this solution are added to 40 ml of water Extraction added to the test solution.

Seeds of the test vegetation are planted in a pot filled with soil and the test solution is sprayed ^{evenly onto the soil surface in an amount of 27.5 micrograms / cm 2.} The pot is poured and placed in a greenhouse. Then it is watered at intervals and observed for seedling emergence, the condition of seedling emergence, etc. for a 3-week period. After the completion of this period, the herbicidal effect of the compound is evaluated based on physiological observation. A scale from 0 to 100 is used, where 0 means no phytotoxicity, while 100 indicates complete destruction. Results of these tests are shown in Table I.

1.30037 / 0604

Herbicidal post-emergence test

The test compound is formulated in the same manner as described above for the pre-emergence test. This formulation is sprayed evenly onto two equal pots of 24 day old plants (approximately 15 to 25 plants per pot) at a dose of 27.5 micrograms / cm ^2. After the plants have dried, they are placed in a greenhouse and then watered at their bases at intervals as required. The plants are periodically examined for phytotoxic effects and the physiological and morphological response to the treatment. After 3 weeks, the herbicidal activity of the compound is evaluated based on these observations. A scale from 0 to 100 is used, with 0 indicating no phytotoxicity and 100 indicating complete destruction. The results of these tests are shown in Table I.

example 1 Production of methyl 5- (2-chloro-4-trifluoromethylphenoxy) -

2-nitrocinnarnate

A. 669 g of 3-hydroxybenzaldehyde, 420 ml of pyridine and 1300 ml of toluene are heated to about 80 C ^0th 55.8 g of malonic acid are added in portions over 30 minutes. The reaction mixture is stirred for a further h, cooled, filtered, rinsed with hexane and air-dried. Yield: 702 g ..

B. 750 g of the 3-hydroxycinnamic acid obtained according to A. in portions of 1.5 l of a methanolic solution

of 85% KOH at 70 to 80 ⁰ C given. The mixture is stirred for 1 hour, stripped, dissolved in 900 ml of DMSO and partially distilled to remove excess solvents. The mixture is ^{cooled to 120 0} C,

130037 / 08Q4

ORIGINAL INSPECTED

whereupon 37 g of K-CO ₃ and 930 g of 1,2-dichloro-4-trifluoromethylbenzene are added. The mixture is heated to 160 ° C. for 18 h, cooled and diluted with 1.8 l of HCl and 3 l of ice water. The dark solid produced is filtered off and recrystallized from ethanol / water. Yield: 895 g.

C. 667 g of 3- (2-chloro-4-trifluoromethylphenoxy) cinnamic acid according to B. are stirred in 1.5 1 acetone, while 2413 g

KpCO., To be added in portions at room temperature. The mixture is cooled in an ice bath and 200 ml of dimethyl sulfate are added. After passing for 1 hour, the mixture is allowed to come to room temperature and stirred overnight and diluted with 8 liters of water. The solid is filtered off, dissolved in methylene chloride, washed to neutral point, dried (MgSO ₄ ) and stripped. Yield: 595 g.

D. 577 grams of methyl 3- (2-chlpr-4-trifluoromethylphenoxy) cinnamate according to C. are dissolved in 12 l of methylene chloride,

cooled with an ice / salt bath to -10 ⁰ C and mixed with 520 ml of a concentrated sulfuric acid over 15 min. 167 g of potassium nitrate are added over 30 minutes. The mixture is stirred at 0 to 10 ^° C. for 5 h and at 20 to 30 ^{° C. overnight.} A further 100 ml of sulfuric acid and 30 g of KNO ~ are added and the solution is stirred for a further 7 hours. The mixture is diluted with 5 l of water, extracted with 3 l of dicblomethane, washed successively with 10% NaHCO ₃ and saturated NaCl solution and dried (MgSO-). The solvent is stripped off and the brown oil obtained (364 g) crystallizes, the sought product having a melting point of 83 to 85 ^° C. being obtained.

130037/0604

Example 2 Preparation of 5- (2-chloro-4-trifluoromethy! Phenoxy) -2-

nitro-ß-bromostyrene

A. 10 g of 3- (2-chloro-4-trifluoromethylphenoxy) cinnamic acid according to 1B. are dissolved in 250 ml of methylene chloride.

4.63 g of bromine in 70 ml of methylene chloride are added dropwise with cooling by means of an ice bath. The mixture is stirred at room temperature until the reaction is complete, stripped, dissolved in 100 ml of methylene chloride and filtered. The filter is stripped and the residue is crystallized to recover 7.5 g of the Oi, β-dibromo adduct of cinnamic acid (2A).

B. 6.2 g of compound 2A. are with 0.87 g of potassium carbonate in acetone at room temperature overnight

touched. The mixture is filtered, stripped and purified by column chromatography, whereby 4.8 g of 3- (2-chloro-.4-trif luormethyl phenoxy) -2-nitro-ß-bromostyrene (2B.) can be obtained.

C. 5.6 g of compound 2B. are dissolved in 25 ml of methylene chloride, cooled to -20 · ⁰ C and treated dropwise with 4 ml of sulfuric acid. After stirring for 30 minutes, 2 ml of concentrated nitric acid are added and the mixture is allowed to slowly come to room temperature. After stirring overnight, the mixture is diluted with 300 ml of methylene chloride and 300 ml of ice water and the organic layer separated, washed successively with water and 10% sodium bicarbonate solution, dried (MgSO ₄ ) and stripped. Purification by chromatography provides the compound sought.

130037/060

Example 3 Preparation of N, N-diethyl-5 (2-chloro-4-trifluoromethyl-

phenoxy) -2-nitrocinnainamide

A. 13.7 g of compound 1B. in 100 ml of anhydrous ether are added dropwise with 5.2 g of oxalyl

chloride stirred. The mixture is refluxed for 8 hours and obtained 3- (2-chloro-4-trifluoromethylphenoxy) -stripped cinnamyl chloride (3A.).

B. To 73.1 g of diethylamine in 250 ml of ethyl acetate, 14.0 g of 3A. admitted. The mixture is stirred at room temperature until the reaction has ended, filtered, washed with water and 10% NaHCO ^ solution and dried (MgSO ₄ ). Purification by chromatography gives 12.2 g of N, N-diethyl-3- (2-chloro-4-trifluoromethylphenoxy) cinnamamide (3B.).

C. 10.0 g of compound 3B. will be according to the procedure according to Example 2C. nitrated, with 2.3 g of the sought

Product can be obtained.

Example 4

Manufacture of 5- (2-chloro-4-trifluoromethylphenoxy) -2- nitro-cinnamic acid ethyl thioester

To 0.81 g Äthylthiol and 1.03 g of pyridine in 100 ml of ethyl acetate at 0 ⁰ C was added dropwise 5.24 g of 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-cinnamyl chloride was added in 60 ml of ethyl acetate. The mixture is stirred at room temperature overnight, filtered, _{washed with water, cold 10% hydrochloric acid, aqueous NaHCO 3} and water, and dried (MgSO.). The solvent is stripped off and the residue is purified by high pressure liquid chromatography (HPLC), 1.7 g of the desired product being obtained.

130037/0604

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ORIGINAL INSPECTED

Ahead - 19 - rs 7 * After ι combat C. 3038083 W. 0 run / Table I. run % P. 70/25 15/25 55/20 t L. Herbicidal activity M. 100/100 0/0 0/0 0/0 - 100/97 100/97 0/25: 0/0 0/0 0/0 0/15 '0/0 45/70 95/25 65/50 75/50 No. 15/50 45/90 100/100 0/0 0/0 0/0 1 100/95 100/100 70/20 100/30 25/80 40/90 IA 70/20 70/45 100/93 α00 / 90 75/100 75/95 IB 100/85: 100/100 100/100 30/55 0/40 0/15 2 100/97 100/100 97/95 100/75 80/100 65/90 2A 50/65 80/80 100/100 30/10 20/35 0/15 3 100/75 100/100 100/90 93/35 65/75 10/40 4th 80/6 0 73/80 100/93 0/0 0/0 0/0 4A 100/60 90/45 0/55 100/85 80/100 65/95 5 0/50 0/20 100/100 90/60 0/45 0/25 5A 100/97 100/75 93/35 92/65 80/70 0/30. 6th 60/20 80/35 100/95 100/80 80/80 25/55 6A 100/92 100/92 100/100. 0/0. 0/0 0/0 7th 100/97 100/100 0/55 97/97 77/85 6 3/52 7A 0/35 .0 / 50 100/100 0/30 0/0 0/0 8th 100/100 80/100 0/25 9 0/30 0/10 9A 10 1OA

L = white goosefoot (Chenopodium album) M = mustard (Brassica arvensis) P = foxtail (Amaranthus retroflexusj C = fingergrass (Digitaria sanguinalis) W = North American paspalum (Echinochloa crusgalli) O = oat grass (Avenua fatua)

ORIGINAL INSPECtSD

Claims (7)

Ι> Κ1Ι> ΕL -HERTBL DR. WOLFCrANG MOaER-ΒθΉέ (PATENT ADVOCATE FROM 1927 - 197B) DR. PAUL OEUFEL. DIPL.-CH EM. DR. ALFRED SCHÖN, DIPL.-CHEM. WERNER HERTEL. DIPL.-PHYS. C 3075 Chevron Research Company 525 Market Street San Francisco, ca.94105 / U S A 5- (2'-chloro-4'-trifluoromethylphenoxy} -2-nitrostyrene derivatives, Process for their preparation and herbicides containing these compounds middle Claims Compound of formula CH = CHR where R has the following meanings: "1 1 -CR, where R is hydroxy, alkoxy with 1 to 4 carbon atoms, optionally substituted by halogen or alkoxy with 1 to 4 carbon atoms, alkyl with 1 to 4 carbon atoms, optionally substituted by halogen or alkoxy with 1 to 4 carbon atoms, 130037/0804 SS-07SO CABLE: · Ττϊ_ .10 ^ 93 -.! 740O "· JJX IM ·. · Aralkoxy of 6 to 8 carbon atoms / amino, optionally substituted by 1 or 2 alkyl groups with 1 to 4 carbon atoms, or aralkyl with 6 to 8 carbon atoms, "- + +
-CO M, where M is a metal or organic cation, "22
-CR, where R is amino, optionally substituted with 1 to 2 alkyl groups having 1 to 4 carbon atoms,. "3 3
-CSR, where R is aralkyl with 6 to 8 carbon atoms or alkyl with 1 to 4 carbon atoms, optionally substituted by halogen or alkoxy with 1 to 4 carbon atoms, -OR, SR, nitro, halogen, amino, substituted by 1 or 2 alkyl groups of 1 to 4 carbon atoms. 2. A compound according to claim 1, characterized in that R is -CR ¹ . 3. A compound according to claim 2, characterized in that R for alkoxy with 1 to 4 carbon atoms, optionally substituted by halogen or alkoxy having 1 to 4 carbon atoms. 4. A compound according to claim 3, characterized in that R ^{1 is} fithoxy. 5. Process for dividing a compound of the formula -Cl CH = CHR 130037/0604 -.- ^ ORIGINAL INSPECTED wherein R has the definitions given in claim 1, characterized in that a compound of the formula .Cl CH = CHR is caused to react with a nitrating agent. 6. Herbicidal agent, characterized by a biologically inert carrier and a herbicidally effective amount a compound of the formula according to claim 1. 7. A method for killing vegetation, characterized in that that on the vegetation or its growing environment a herbicidally effective amount of a compound of the formula according to claim 1 .wird is applied. 130037/0 * 04 INSPECTED