CS251084B2 - Herbicide and method of its active component production - Google Patents

Description

The reaction is suitably carried out at a temperature above room temperature, for example 100 ° C or at reflux temperature. Suitably the reaction is carried out in the presence of an acid, for example acetic acid; it can also serve as a reaction solvent.

The compound of formula (I) may be obtained from the reaction mixture in which it was prepared by known methods.

The compounds of the invention have one or more asymmetric carbon atoms. The present invention includes all optically active isomers and racemic mixtures thereof. In the examples below, unless otherwise indicated, the compounds prepared are racemic mixtures.

The starting materials can be prepared by various modifications of known procedures.

Examples of suitable reaction schemes for preparing various compounds of · the formula II are shown below [M 'represents O or · S; Alk is C ₁ _ _s alkyl, Hal is halogen (e.g., Cl), R ⁹ is H or ^ _8alkyl and X Y, R 1, R ² and R ³ are as defined above and Z is O, S or NR ', R' is hydrogen or C 1-8 alkyl].

1) hydrolysis

2) + HalCH (R ⁹ ) -COOAlk

Μ'-CM-P-OcC-((R) COOAlk No 12

R (YV) ^h2n, 251084

Analogously the compound of formula ^XVIII O \ i и M-CH-P-OAlk

R <RZ (XVHt) where

X ‘denotes H, Cl or Br, and

Y, R ¹ , R ² , Alk and M "are as defined above, prepared by reacting a compound of Formula XII or XIII with the corresponding nitrophenol or -thiol. The nitro compound of formula XVIII may be hydrogenated to the corresponding amino compound and / or halogenated and allowed to react further with a compound of formula R ³ ZH optionally hydrolyzed and reacted with a compound of the formula HalCH ^(R9) COOAlk as indicated above for the amino compound of formula XV . The starting materials and reagents used in the above procedures are known or, if they are not known, can be prepared by procedures analogous to those described above or by known procedures.

The novel compounds of the formula I are used for weed control in pre- and / or post-emergence treatments. The compounds may be applied in the form of dusts, granules, solutions, emulsions, wettable powders and suspensions. The application of the compounds of the invention may be carried out by conventional methods to weeds or their locus using a herbicidally effective amount of the compounds, usually from about 100 g to 10 kg / ha.

The optimal dosage of the compounds of the invention is determined by any of the conventional methods of the art, such as a greenhouse test or small field tests. However, generally, the results obtained show that the compounds are applied in an amount of about 0.01 to 5 kg / ha (e.g. 0.011, 0.036, 0.11 or 0.36 kg / ha for post-emergence application and 0.11, 0.36). , 1.1 or 3.6 kg / ha for pre-emergence application).

The compounds of the invention are effective against grass weeds. In general, the compounds exhibit higher herbicidal activity against broadleaf plants. Species of broadleaf plants (weeds) to which the compounds of the invention exhibit herbicidal activity include, but are not limited to, mustard (Brassica spp.), Goosefoot (Amaranthus spp.), Abutilon (Abutilon theophrasti), common durman (Datura stramonium), Xanthium spp., Cassia obtusifolia and Ipomoea purpurea Many of the compounds of formula I have excellent compatibility with cereals (maize).

Because of their broad spectrum of activity against broadleaf weeds, the compounds of the present invention can advantageously be combined with grass herbicides to achieve a broad spectrum of post-emergence activity in many cultures. Examples of herbicides that may be combined with the compounds of the present invention are selected from the group consisting of carbamates, thiocarbamates, chloroacetamides, dinitroanilines, benzoic acids, glycerin ethers, pyridazinones, uracils and ureas to control a significant number of weeds.

The term "herbicide" as used herein means an active substance that affects the growth of plants, acts phytotoxically or has plant growth-regulating properties by slowing it down or destroying the plant.

Preferred substituents of the compound of formula I are:

X is F or Cl, more preferably F,

Y is F or Cl, especially Cl,

R ¹ is H or C _1-2 alkyl and

R ² and R ³ are as defined above.

The compounds of formula I are commonly used as herbicidal compositions together with agriculturally suitable diluents. These compositions are also included within the scope of the invention. They may contain, in addition to the compounds of the general formula I as active ingredients, further active ingredients such as herbicides. They may be in the form of solid or liquid, for example in the form of wettable powders, emulsifiable concentrates, water-dispersible suspension concentrates, dusts, granules and sustained release forms, by the addition of a conventional diluent. These compositions can be prepared in conventional manner, for example by mixing the active ingredient with a diluent and optionally adding other ingredients such as surfactants.

By diluent is meant herein liquid or solid agriculturally acceptable substances which can be added to the active ingredient and thereby converted into a form that is easier or better to apply, optionally to achieve appropriate or desired efficacy. It can be, for example, talc, kaolin, diatomaceous earth, xylene or water.

Self-formulations which are applied in sprayable forms such as water-dispersible concentrates or wettable powders may contain surfactants such as wetting or dispersing agents, for example the formaldehyde-naphthalenesulfonate condensation product, alkylarylsulfonate, ligninsulfonate, aliphatic alkylsulfonate, ethoxylated alkylphenol and ethoxylated alkylphenol. .

In general, the compositions comprise from 0.01 to% by weight of the active ingredient, to 20% by weight of the agriculturally acceptable surfactant and from 99.99 to 10% by weight of the (solid or liquid) diluent (s).

The active ingredient comprises at least one of the compounds of the formula I or a mixture thereof with other active ingredients. The concentrates of the compositions contain between about 2 to 90% by weight, preferably between about 5 to 70% by weight, of active ingredient. For example, the dosage forms may contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight, of the active ingredient.

The following examples illustrate the process of the invention. The temperature is given in degrees Celsius and the percentages and parts are by weight. TM means room temperature.

Example of composition 1.

A wettable powder of parts of the compound of formula I is ground with 3 parts of lauryl sulfate, 5 parts of sodium lignin sulphonate, 22 parts of silica and 45 parts of fine kaolin until the particles have a mean size below 5 microns. The wettable powder thus prepared is diluted with water before use.

Example of resource 2:

The emulsifiable concentrate of parts of the compound of formula (Г), 65 parts of xylene, 10 parts of the reaction product of alkylphenol with ethylene oxide and calcium dodecylbenzenesulfonate was thoroughly mixed until a homogeneous solution was obtained. The resulting concentrate is diluted with water before use.

Process for preparing compounds

Example 1

N- {5- [cis- (ethyl-P-methylphosphino) ethoxy] -2,4-dichlorophenyl; tetrahydrophthalimide

Ethyl β-methyl [α- (2,4-dichloro-5-aminophenoxy) ethyl] phosphinate (500 mg, 1.6 mmol) was dissolved in glacial acetic acid. To the solution was added 3,4,5,6-tetrahydrophthalic anhydride (292 mg, 1.9 mmol). The mixture was heated under nitrogen at 100 ° C overnight and then at 140 ° C for an additional 6 hours. Cooling to RT, adjusting the pH to 5-6 with potassium carbonate, diluting with water and extraction with methylene chloride. The extracts were combined, dried over sodium sulfate and evaporated to dryness, followed by purification by thin layer chromatography (TLC) to give N- [5- [α- (ethyl-β-methylphosphino) ethoxy] -2,4-dichlorophenyl] tetrahydrofthalimide, MS m / e 446.3 (M ⁺ ) (Compound 1, Table A).

Example 2

N- [5- (ethyl-P-ethylphosphinomethoxy) -4-chloro-2-fluorophenyl] tetrahydro-phthalimide

A mixture of ethyl P-ethyl (2-chloro-4-fluoro-5-amino-phenoxy) methylphosphinate (0.77 g, 2.61 mmol) and 3,4,5,6-tetrahydrophthalic anhydride (0.52 g, 3.39) mmol) in 5 ml of acetic acid was heated at reflux for 9 hours. Excess anhydride and acetic acid were removed in vacuo. The oily product was purified by TLC to give N- [5- (ethyl-P-ethylphosphinomethoxy) -4-chloro-2-fluorophenyl] tetrahydrophthalimide, MS m / e 429 (M +) (Compound 13, Table A).

NMR (CDCl 3) δ

8.87, 8.65 (t, t, 3H, P - CH2 --CH3),

8.70 (t, 3H, O - CH2 --Nz),

5.93 (q, О — СНг — СНз),

5.82 (d, 2H, [beta] -O-CH2-NH2), [3.15 (d, 1H), 2.77 (d, 1H) -mag. Н].

Example 3

In analogy to Example 1 or 2, the following compounds of formula (Ig) are obtained by reacting 3,4,5,6-tetrahydrophthalic anhydride with the corresponding aminophenoxy compound of formula (II).

Table A

^ №НОЮСоЧСЛ> ЬиЗГ <РСЩС »<1 С; СЛ ^ ССГ <'РОСОООХ | ГОСЛ» ДСО ^ НО и

Cl Cl СНз СНз СНгСНз 446, Г Cl Cl СНгСНз СНз СНз 446.27 H Cl СНгСНз СНз СНз 411.0 Cl Cl Η СНз СНз 418.22 Cl Cl СНз СНгСНз СНз 446.29 Cl Cl СНз СНгСНгСНз СНз 460,30 Cl Cl СНз СНз СНгС (О) ОСНз 490.28 Cl Cl СНз СНгСНз СНгС (О) ОСНз 504.31 Cl Cl СНгСНз СНз СНгС (О) ОСНз 504.31 F Cl СНгСНз СНз СНгСНз 444 Cl Cl СНгСНз СНгСНз СНз 460,00 Cl Cl н СНз СНгС (О) ОСНз 476.25 F Cl н СНгСНз СНгСНз 429.0 F Cl н СНгСНз СН (СНз) г. 443 F Cl СНз СНгСНгСНз СНгСНз 457 F Cl СНз СНгСНз СНгСНз 443 F Cl СНз СНз СНгСНз 429 F Cl СНгСНз СНгСНз СНгСНз 457 F Cl Н СНгСНз СНгСН (СНз) г. 457 F Cl н СНгСНз СНгСНгОСНз 459 F Cl СНгСНз СНз СНгСН = СНг 455 F Cl СНз СНгСНгСНз СН2СН2ОСН5 487 F Cl СНгСНз СНз СНгСНгОСНз 473 F Cl СНгСНз СНз СНг = СН 453.6 H Cl СНгСНз СНгСНз СНз 425.8 H Cl СНгСНз СНгСНз СНгСНз 439.9 Cl Cl СНз СНз СНз 432.2 F Cl Н СНз СНгСНз 415.8 F Cl СНз СН (СНз) г. СНгСНз 457.8 F Cl СН2СН2СН2 СНз СНгСНз 457.8 F Cl Н СНгСНгСНз СНз 429.8 F Cl Н СНгСНз СНз 415.8 H Cl СНгСНз СНз СНгСНз 425.8 H Cl Н СНгСНз СНгСНз 411.8 H Cl СНз СНгСНгСНз СНгСНз 439.9 H Cl СНз СНгСНз СНгСНз 425.8 H Cl СНз СНгСНз СНз 411.8 H Cl Н СНгСНз СНз 397.8 H Cl СНгСНз СНз СНгС (1) ОСНз 487.8 F Cl С2Н5 СНз СНг — СН (СНз) г. 471.89 F Cl С2Н5 СНз СН (СНз) г. 457.87 F Cl 11С3Н7 СНз СНз 443.84 F Cl н пСзН7 С2Н5 433.7

The compounds listed in Table A are still characterized as follows:

Compound No. 19

NMR (CDCl3) ε

9.04 [d, 6H, CH (CH 3) 2],

8.92, 8.54 (tt, 3H, P - CH2 --CH5),

8.20 (m, 8H, CH2 --CH2, P - CH2 - CH3, O - CH2 - CH / CH3 / 2),

5.77 (d, 2H, OCH 2 -P), [3.15, (d, 1H), 2.80 (d, 1H) -aromatic Hj.

Compound No. 20

NMR (CDCl3) ε

8.92, 8.52 (tt, 3H, P - CH2 --CH3),

8.16 (m, 6H, CH2 --CH2, P - CH2 - CH3),

6.70 (s, 3H, O-CH 3),

6.47 (t, 2H, O-CH2-CH2-O-CH3),

5.87 t, 2H, O-CH2-CH2-O-CH3),

5.70 (d, 2H, O - CH2 --P], [3.10 (d, 1H), 2.77 '(d, 1H) - aromatic H].

Compound No. 25

NMR (CDCl3) ε

8.78 [m, 6H, P-CH2-CH3,

O — CH (CH2CH3) —P],

8.07 [m, 8H, CH2-CH2, P-CH2-CH3,

O — CH (CH2CH3j — P], ”

6.32, 6.12 (dd, 3H, P-OCH 3),

5.42 [m, 1H, O-CH (CH2CH3j-P),

2.87 (m, 3H, aromatic H).

Compound No. 26

NMR (CDCl 3) ε

8.77 [m, 9H, O-CH2-CH3, P-CH2-CH3, O-CH (CH2 (CH2-P), '

8.20 [m, 8H, - CH2 --CH2, P - CH2 --CH5,

O — CH (CH2CH3] - P],

5.70 [m, 3H, O-CHCCH2CH3-P,

About — CH2 — CH3], ’

2.87 (m, 3H, aromatic H).

3.5 mmol) was heated for 3 hours. The dioxene is then removed in vacuo to give the corresponding isocyanate. The residue was taken up in methylene chloride (35 mL). 2- (Eloxycarbonyl) hexahydropyridine (0.754 g, 0.75 mL, 4.8 mmol) was added and the mixture was stirred at RT overnight. The reaction mixture was diluted with methylene chloride, washed with water, dried and evaporated to dryness. The resulting urea derivative (1.5 g, 3.2 mmol) was dissolved in ethanol (15 mL). 2N hydrochloric acid (20 ml) was added, and the solution was heated to reflux for 5 hours and then to 90 ° C overnight. The ethanol was removed in vacuo and the residue was diluted with water, extracted with methylene chloride (3 times). The combined extracts were dried and evaporated to dryness. The crude product is purified by TLC to give the title compound. MS m / e 446 (M &lt; + &gt;) (Compound 54).

Example 5 l-Methyl ^---! | 5- [a (ethyl-P-methylisulfonyl) -n-propoxy] -2,4-dichlorophenyl} hydantoin

A mixture of ethyl-1-methyl-1- (2,4-dichloro-5-aminophenoxy) -phenylphosphinate (2.20 g, 6.7 mmol) and trichlorofluorochloroform (1.60 g, 0.97 ml, 8.1 mmol) in dioxane (50 mL) and III-amine (0.81 g, 1.1 mL, 8.1 mmol) was heated for 3.5 hours. The dioxane was evaporated in vacuo and the resulting isocyanate was taken up in melhylene chloride (60 mL). Add diethylamine (1.02 g, 1.4 mL, 10.1 mmol) and methyl (methylaminoacetate) -hydrochloride (1.40 g, 10.1 mmol) and stir at RT for 1 h. The reaction mixture was diluted with methylene chloride, washed with water, dried and evaporated to dryness. To the resulting urea derivative (2.5 g) dissolved in ethanol (15 mL) was added 2N hydrochloric acid [20 mL] and the mixture was stirred at RT for about 60 hours. The mixture was then heated to reflux for 7 hours and further stirred at RT overnight. The ethanol is then removed in vacuo, the residue is diluted with water and extracted with methylene chloride. The combined extracts were dried and purified by TLC to give the title compound, MS m / e 423 (M +) (Compound 55). _

Example 6 1-Methyl-3- {5- [α- (ethyl-4-methylphosphino) -n-propoxy] -4-chloro-2-fluorophenyl] -hydantoin

Ethyl P-methyl-1- (2-chloro-4-fluoro-5-aminophenoxy) propyl phosphinate (1.00 g, 3.2 mmol) and trichloromethyl chloroformate (0.76 g, 0.46) are reacted in the same manner ml, 3.9 mmol) and the resulting isocyanate was treated with methyl (amino amino) hydrochloride (0.67 g, 4.8 mmol) and the resulting urea derivative (3.2 mmol) was heated with 2N hydrochloric acid (8 mL). ) and cleans for

Example 4

3- [5 - [[[Ethyl-P-methylphosphino) n-propoxy] -4-chloro-2-fluorophenyl] -1,5-etramethylenehydantoin

A mixture of ethyl-β-methyl-1- (2-chloro-4-fluoro-5-aminophenoxy) propyl phosphate (1.00 g,

3.2 mmol) and 1-chloromethyl-chloroformate (0.76 g, 0.46 mL, 3.9 mmol) in dioxane (50 mL) and 1-triethylamine (0.36 g, 0.49 mL, 251084) to give the title compound, MS m m / e 406 (M +) (Compound 56).

Example 7

4- {5- [α- (Ethyl-β-methylphosphino) -n-propoxy] -4-chloro-2-fluorophenyl] -1,2-tetramethylenetri. zolidine-3,5-dione

Following the procedure of Example 4, ethyl P-methyl-1- (2-chloro-4-fluoro-5-aminophenoxy) propylphosphinate was reacted with trichloromethylchloroforminate and the resulting isocyanate was reacted with N-ethoxycarbonylhexahydropyridazine hydrochloride to give the title compound. (Compound 57).

Example 8

2- tert -Butyl-4- [5- (methyl-β-ethylphosphinomethoxy) -4-chloro-2-fluorophenyl] -D 2 -1,3,4-oxadiazolin-5-one

A mixture of methyl-P-ethyl- [2- (chloro-4-fluoro-4- [5- (N'-pivaloylhydrazino) phenoxy] methylphosphinate (3.2 mmol), trichloromethylchloroformate (3.9 mmol) and triethylamine (3). (5 mmol) in dioxane (50 mL) was heated for 3.5 h. The dioxane is then removed under vacuum. The product was diluted with methylene chloride, washed, dried, evaporated to dryness and purified by TLC to give the title compound (compound 58).

Example 9

3-tert-Butyl-1- '5- [α- (methyl-β-methylphosphino) propoxy] -2,4-dichlorophenyl] -2,2,2,4-triazol-5-one

A mixture of methyl-p-methyl-l- (2,4-dichlOT 5hydrazin ^{ί-o-phenoxy)} proρylfosfinátu (9.6 mmol) and pivaloylmočoviny (9.6 mmol) in decahydronaphthalene (decalin, 12 ml) was heated to reflux temperature flow with stirring for about 8 hours, followed by the reaction of Gold-Aubert et al. [Helvetica Chimica Acta 47 (5 (): 1 188 (1964)) to give the title compound (compound 59) after purification.

Example 10

1- [5-Methyl-β-ethylphosphinomethoxy) -4-chloro-2-t-thiophenyl] -A 2 -1,2,4-thiazolm-5-one

Following the procedure of Example 9, methyl-P-ethyl (2-chloro-4-fluoro-5-hydroxy-5'-hydroxy-phenoxy-methyl) -Osinate was reacted with formyl urea to give the title compound [Compound 60].

Example 11

4-Methyl-l- [5- (methyl-p-methoxy ethyl phosphonate amino) -4-chloro-2-fluorophenyl] -Δ ² -1,2,4-trimethyl-5-one iazolin-

To the title compound of Example 10 (2.5 mmol) was added methyl odide (3.0 mmol), sodium hydride (2.5 mmol) and dimethylformamide (15 mL). The mixture was heated at 80 ° C for 3 hours. After cooling to RT, the reaction mixture was poured into water and extracted with methylene chloride. The combined extracts were washed with water, dried, evaporated to dryness and purified by TLC. The title compound (Compound 61) was obtained.

Example 12

N- [5- (Ethyl-P-ethylphosphomethylthio) -4-chloro-2-fluorophenyl) tetrahydrophthalimide

Following the procedure of Example 2, 2-chloro-4-fluoro-5-amino-enylthiol is reacted with ethyl-P-ethyl (methylsulfonyloxymethyl) phosphinate to give ethyl-P-ethyl (2-chloro-4-fluoro-4-aminophenyl) enylthio) methylphosphinate, which is then reacted with 3,4,5,6-tetrahydro-octanhydride to give the title compound.

Herbicidal effect

Example 13

The pre-emergence herbicidal activity of compounds 1 and 2 according to the invention was tested as follows: selected weed seeds were planted and the soil was pickled with a solution of water (17%), a surfactant (0.17%) and a test compound of 11.2 kg / ha and 3,696 kg / ha. Evaluation was performed two weeks after treatment. In the test at a concentration of 11.2 kg / ha, the grasses (GR) were used, the grass leg, Sorghum bicolor and deaf oats and broadleaf plants (BL) of bitterweed, mustard, eggplant and Abutilon. In a test using a concentration of 3.386 kg / ha, grasses were used, grass roots, corn rootworm, deaf oats and roe and broadleaf mustard, goosefoot, abutilon, durman, beetroot, Kassie and bitterweed . The average preemergence activity of both compounds is shown in Table B below.

Example 14

The post-emergence herbicidal activity of compounds 1 and 2 was tested as follows: The weed seedlings were sprayed with water / acetone solution (1: 1), surfactant (0.5%) and test compounds at 11.2 kg / ha and 3,696 kg / hectare. Evaluation was performed two weeks after spraying. In the test at a concentration of 11.2 kg / ha, grasses (GR) were used, the green leg, the corn leg, Sorghum bicolor .251084

14 and deaf ov-es a. broadleaf plants (BL). In the test at a concentration of 3.696 kg / ha ', grass of green leg, hedgehog corns leg, rumpet and deaf oats and broadleaf plants were used to feed hens, goosefoot, abutilon, beet and Kassie. The average post-emergence activity of compounds 1 and 2 is shown in Table B below.

Example 15.

Following the procedure of Example 13, TABLE B% Mean Herbicidal Efficacy was tested for compounds 13, 15 and 20. Their pre-emergent herbicidal activity was determined at a concentration of 11.2 kg / ha and 3.666 kg / ha. The average potency of the three compounds is shown in Table B.

Following the procedure of Example 14, the postemergence activity of compounds 13, 15 and 20 was determined at a concentration of 11.2 kg / ha for grasses and 11.2 and 3.666 kg / ha for broadleaf weeds. The average efficacy is shown in Table B.

Preemergent Postemergent

Compound kg / ha GR BL GR BL 1 11.2 77 100 ALIGN! 67 100 ALIGN! 3,696 63 93 73 100 ALIGN! 2 11.2 82 100 ALIGN! 100 ALIGN! 90 3,696 89 100 ALIGN! 88 100 ALIGN! 13 11.2 92 100 ALIGN! 100 ALIGN! 100 ALIGN! 3,696 90 100 ALIGN! - 100 ALIGN! 15 Dec 11.2 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! 3,696 84 100 ALIGN! - 100 ALIGN! 20 May 11.2 93 100 ALIGN! 87 100 ALIGN! 3,696 76 . 100 ALIGN! - 100 ALIGN!

OBJECT OF INVENTION

Claims (4)

OBJECT OF INVENTION What is claimed is: 1. A herbicidal composition comprising, as an active ingredient, a compound of the formula (I): EMI10.1 wherein: X and Y are each independently hydrogen or halogen, R 1 is hydrogen or C _1-3 alkyl, R 2 represents a C ₃ alkyl, R ³ represents C 1-4 alkyl, CH 2 -C = CH, CH2-CH-CH2, (C1-4alkoxy) -carbonyl-C1-4alkyl or (C4-4alkoxy) -C1-4alkyl. 2. A composition according to claim 1, characterized in that it comprises as active ingredient a compound of formula I wherein R ³ represents Ci_4alkyl, CH2CH-CH2, (Ci ^ alkoxy) carbonyl-Ci_4alkyl or (C ₄ alkoxy) C _'4 alkyl , and XY, R 1, R 2 are as defined in 1. 3. A process for the preparation of a compound of formula I as active ingredient according to claim 1, characterized in that the compound of formula II is reacted X, Y, R 1, R 2 and R 3 are as defined in item 1, with a compound of formula III 4. A method according to Claim 21, characterized in that as starting material a compound of formula II · wherein R ³ represents Ci_4alkyl, CH 2 -CH = CH 2, (C ₄ alkoxyj-carbonyl- (Ci_4alkyl), or (Ci_4alkoxy) - C 1-4 alkyl, X, Y, R 1 and R ² are as defined in item 1.