DE3725939A1 - Heterocyclically substituted phenyl sulphamates, their preparation, and their use as herbicides and plant growth regulators - Google Patents

Abstract

Compounds of the formula I or their salts <IMAGE> in which R<1> is substituted alkyl; (substituted) alkenyl; (substituted) alkynyl; R<2> is halogen; nitro; (substituted) alkyl or (substituted) alkoxy; R<3> is hydrogen; alkyl; alkenyl or alkynyl; and R<4> is a heterocyclic radical of the formulae <IMAGE> where E is CH or N, and n is 0, 1, 2 or 3, have outstanding herbicidal and plant-growth-regulating properties.

Description

Heterocyclically substituted sulfamic acid phenyl esters, Process for their preparation and their use as Herbicides and plant growth regulators.

It is known that heterocyclic substituted Phenoxysulfonylureas herbicidal and have plant growth regulating properties (see EP-A 4 163, EP-A 1 65 572).

However, these have disadvantages when used, such as for example, high persistence or insufficient Selectivity.

It has now been found that heterocyclically substituted Phenyl sulfamic acid, special in the phenyl ester part Contain alkoxycarbonyl groups, as herbicides and Plant growth regulators are particularly suitable.

The present invention therefore relates to Compounds of formula (I) or their salts

wherein
R¹ (C₁-C₈) alkyl which is substituted one or more times by halogen or once or twice by (C₁-C₄) alkoxy; (C₂-C₈) alkenyl, (C₂-C₈) alkynyl, both of which may optionally be substituted one or more times by halogen or once or twice by (C₁-C₄) alkoxy,
R² independently of one another halogen; Nitro; (C₁-C₄) alkyl or (C₁-C₄) alkoxy, both of which may optionally be substituted one or more times by halogen,
R³ is hydrogen; (C₁-C₈) alkyl; (C₂-C₈) alkenyl or (C₂-C₈) alkynyl,
R⁴ is a heterocyclic radical of the formulas

where E = CH or N,
n 0, 1, 2 or 3,
R⁵, R⁶ independently of one another hydrogen; Halogen; (C₁-C₄) alkyl or (C₁-C₄) alkoxy, both of which may optionally be halogenated one or more times; Di- (C₁-C₄) alkoxy- (C₁-C₂) alkyl; Cyclopropyl, -OCHR⁸COOR⁹; -NR⁹R¹⁰ or (C₁-C₄) alkylthio,
R⁷ (C₁-C₄) alkyl,
R⁸ is hydrogen or (C₁-C₄) alkyl and
R⁹, R¹⁰ are independently hydrogen; (C₁-C₄) alkyl; (C₂-C₄) alkenyl or (C₂-C₄) alkynyl
mean.

The compounds of formula I can form salts in which the hydrogen of the -SO₂-NH group by one for the Agriculture suitable cation is replaced. These salts are generally metal, especially alkali,  Alkaline earth metal, optionally alkylated ammonium or organic amine salts. They are preferably inert Solvents such as B. water, methanol or acetone Temperatures of 0-100 ° C produced. Suitable bases for Preparation of the salts according to the invention are, for example Alkali carbonates such as potassium carbonate, alkali and Alkaline earth hydroxides, ammonia or ethanolamine.

Preferred compounds of formula I are those in which R¹ is (C₁-C₄) alkyl substituted as described above or (C₃-C₄) alkenyl which may be substituted as described above; R² is halogen, (C₁-C₃) alkyl or (C₁-C₃) alkoxy, which may be substituted as described above; n = 0, 1 or 2; R³ is hydrogen, (C₁-C₄) alkyl or allyl; R⁴ is a residue of the formula

and R⁵ and R⁶ independently of one another halogen, (C₁-C₄) alkyl or (C₁-C₄) alkoxy, both of which Halogen may be substituted, as well as their Salts.

Halogen is preferably fluorine, chlorine or bromine. Are halogenated alkyl or halogenated alkoxy in particular to understand the radicals CF₃, CH₂-CH₂Cl, CH₂CH₂Br, OCF₂H, OCH₂CF₃. Halogenated alkenyl or halogenated alkynyl means in particular CH₂CH = CHCl, CH₂CCl = CCl₂, CH₂-C≡CCH₂-Cl.

Particularly preferred compounds of formula (I) are those in which R¹ is (C₁-C₄) alkyl substituted as described above or (C₃-C₄) alkenyl which may be substituted as described above; n = 0; R³ is hydrogen, R⁴ is a radical of the formula

and R⁵ and R⁶ independently of one another chlorine, bromine, (C₁-C₄) alkyl, Are (C₁-C₄) alkoxy, OCF₂H, OCH₂CF₃ or CF₃, and their salts.

The present invention furthermore relates to Process for the preparation of compounds of general Formula (I), characterized in that

• (a) a compound of formula (II) with a compound of formula (III) implements, or
• (b) a compound of formula (IV) with a chlorosulfonylurea of the formula (V) implements, or
• (c) a substituted benzoic acid of the formula (VI) with an alkylating reagent of the formula (VII) R¹-X (VII), where X is a nucleofugic leaving group such as. B. halogen, alkyl-SO₂-O- or tosyl is implemented.

The implementation of the compounds of the formulas (II) and (III) is preferably carried out in inert aprotic solvents, such as B. acetonitrile, dichloromethane, toluene, Tetrahydrofuran or dioxane at temperatures between 0 ° C and the boiling point of the solvent.

The phenoxysulfonyl isocyanates of the formula (II) can be by methods known in principle from the corresponding Salicylic acid esters of the formula (IV) and Produce chlorosulfonyl isocyanate in a simple manner (see G. Lohaus, Chem. Ber. 105, 2791 (1972)).

The starting materials of the formula (III) are known or have not been used produce themselves according to known methods, e.g. B. by cyclization of corresponding guanidine derivatives with appropriately substituted 1,3-diketones, compare e.g. B. "The Chemistry of Heterocyclic Compounds", Col. XVI (1962) and Supplement I (1970), or by derivatization of Cyanuric chloride, cf. e.g. B. "The Chemistry of Heterocyclic Compounds ", L. Rapaport:" s-Triazines and Derivates "(1959).  

The implementation of the compounds (IV) with the Chlorosulfonylureas (V) are preferably carried out in inert solvents such as B. dichloromethane, Tetrahydrofuran, dioxane or dimethoxyethane Temperatures between -10 ° C and 80 ° C in the presence of a Base as an HCl-binding agent. As bases can Alkali or alkaline earth carbonates or bicarbonates such as B. K₂CO₃, NaHCO₃, Na₂CO₃ or tertiary amines such as. B. pyridine or triethylamine can be used.

The salicylic acid esters (IV) are known from the literature or can be produced by methods known from the literature will. The chlorosulfonylureas (V) are from the Amines of the formula (III) and chlorosulfonyl isocyanate accessible (EP-A 1 41 199).

The implementation of the benzoic acids (VI) with the reagents of the Formula (VII) is used in inert solvents such as. B. Dimethylformamide or dimethyl sulfoxide, preferably in Presence of an auxiliary base such as B. triethylamine or Tetramethylammonium hydroxide pentahydrate, at temperatures between 0 ° C and the boiling point of the solvent carried out.

The compounds of formula I according to the invention have a excellent herbicidal activity against a broad Spectrum of economically important mono- and dicotylers Harmful plants. Also difficult to fight perennials Weeds made from rhizomes, rhizomes or others Drive out permanent organs, the active ingredients are good detected. It does not matter whether the substances in the Pre-sowing, pre-emergence or post-emergence procedures applied will. Some representatives are examples the monocotyledonous and dicotyledonous weed flora, which are caused by the compounds of the invention can be controlled, without being limited to certain by the naming Species should be done.  

On the side of the monocot weed species, e.g. B. Avena, Lolium, Alopecurus, Phalaris, Echinochloa, Digitaria, Setaria etc. as well as Cyperus species from the annual group and on the part of the perennial species Agropyron, Cynodon, Imperata as well as sorghum etc. and also Persistent cyperus species well recorded.

This extends to dicotyledon weed species Spectrum of action on species such as B. Galium, viola, Veronica, Lamium, Stellaria, Amaranthus, Sinapis, Ipomoea, Matricaria, Abutilon, Sida etc. on the annual page as well as Convolvulus, Cirsium, Rumex, Artemisia etc. with the Perennials.

Under the specific culture conditions in the rice occurring weeds such as. B. Sagittaria, Alisma, Eleocharis, Scirpus, Cyperus etc. are from the Active substances according to the invention are also outstanding fought.

Are the compounds of the invention before germination applied to the earth's surface, so either Prevention of weed seedlings completely, or the weeds grow up to the cotyledon stage, but then stop growing and die finally complete after three to four weeks from. When applying the active ingredients to the green ones Plant parts in the post-emergence process also occur very much a drastic growth stop soon after treatment one, and the weed plants remain in the for Application time available growth stage or die more or less quickly after a certain time from, so that one for crops harmful weed competition very early and sustainably the use of the new compounds according to the invention can be eliminated.  

Although the compounds of the invention are one excellent herbicidal activity against mono- and dicotyledon weeds are cultivated plants economically important cultures such as B. wheat, Barley, rye, rice, corn, sugar beet, cotton and soy only slightly or not at all damaged. The The present compounds are suitable for these reasons very good for selective control of unwanted Plant growth in agricultural crops.

In addition, the compounds of the invention growth regulatory properties in crops on. They regulate the plant's own Metabolism and can thus facilitate harvesting such as B. by triggering desiccation, abscess and Growth compression can be used. They are also suitable also for general control and inhibition of undesirable vegetative growth without losing the plants kill. An inhibition of vegetative growth plays a major role in many mono- and dicotyledon cultures, because this reduces or completely prevents storage can be.

The agents according to the invention can be used as wettable powder, emulsifiable concentrates, sprayable solutions, Dusts, mordants, dispersions, granules or Microgranules used in the usual preparations will.

Spray powders are evenly dispersible in water Preparations in addition to the active ingredient except where appropriate a diluent or inert wetting agent, e.g. B. polyoxethylated alkylphenols, polyoxethylated Fatty alcohols, alkyl or alkylphenyl sulfonates and Dispersants, e.g. B. sodium lignosulfonate, 2,2'-di naphthylmethane-6,6′-disulfonic acid sodium,  dibutylnaphthalenesulfonic acid sodium or also Contain oleoylmethyl tauric acid sodium. The production takes place in the usual way, such as. B. by grinding and mixing of the components.

Emulsifiable concentrates can e.g. B. by dissolving the Active ingredient in an inert organic solvent, e.g. As butanol, cyclohexanone, dimethylformamide, xylene or also higher-boiling aromatics or hydrocarbons Addition of one or more emulsifiers produced will. In the case of liquid active ingredients, the Part or all of the solvent content is eliminated. As For example, emulsifiers can be used: Alkylarylsulfonic acid calcium salts such as Ca-dodecylbenzenesulfonate or nonionic emulsifiers such as Fatty acid polyglycol esters, alkyl aryl polyglycol ethers, Fatty alcohol polyglycol ether, propylene oxide-ethylene oxide condensation products, Fatty alcohol-propylene oxide-ethylene oxide condensation products, Alkyl polyglycol ether, Sorbitan fatty acid esters, polyoxethylene sorbitan fatty acid esters or polyoxethylene sorbitol ester.

Dusts can be obtained by grinding the active ingredient with finely divided, solid substances e.g. B. talc, natural Clays such as kaolin, bentonite, pyrophillite or diatomaceous earth receive.

Granules can either by spraying the active ingredient on adsorbable, granulated inert material be produced or by applying Active substance concentrations by means of binders, e.g. B. Polyvinyl alcohol, sodium polyacrylic acid or also Mineral oils on the surface of carriers such as sand, Kaolinite or granulated inert material. Can too suitable active substances in the for the production of Fertilizer granules in the usual way, if desired in Mix with fertilizers, granulated.  

The active ingredient concentration in wettable powders is e.g. B. about 10 to 90 wt .-% the rest of 100 wt .-% consists of usual formulation components. With emulsifiable Concentrates can the active ingredient concentration about 5 to 80 wt .-% be. Contain dusty formulations usually 5 to 20 wt .-% of active ingredient, sprayable Solutions about 2 to 20 wt .-%. With granules it depends Active ingredient content partly depends on whether the effective Connection is liquid or solid and which Granulation aids, fillers, etc. can be used.

In addition, the active ingredient formulations mentioned contain where applicable, the usual liability, network, Dispersing, emulsifying, penetrating, solvent, filling or carriers.

To be used in the commercial form existing concentrates, if necessary, in a customary manner diluted, e.g. B. with wettable powders, emulsifiable Concentrates, dispersions and sometimes also at Microgranules using water. Dusty and granulated preparations and sprayable solutions are usually no longer used before other inert substances diluted.

With the external conditions such as temperature, humidity u. a. the required application rate varies. she can fluctuate within wide limits, e.g. B. between 0.005 and 10.0 kg / ha or more of active substance, preferably it is however between 0.01 and 5 kg / ha.

Mixtures or mixed formulations with others Active ingredients, such as B. insecticides, acaricides, herbicides, Fertilizers, growth regulators or fungicides possibly possible.

The invention is illustrated by the following examples.  

Formulation examples

A. Dusts are obtained by 10 Parts by weight of active ingredient and 90 parts by weight of talc or Mixes inert material and crushes it in a hammer mill.

B. A water-dispersible, wettable powder is obtained by adding 25 parts by weight of active ingredient, 64 Parts by weight of kaolin-containing quartz from inert material, 10 Parts by weight of lignosulfonic acid potassium and 1 Part by weight of oleoylmethyl tauric acid sodium as a and dispersant mixes and in a pin mill grinds.

C. An easily dispersible in water Dispersion concentrate is obtained by 20 Parts by weight of active ingredient with 6 parts by weight Alkylphenol polyglycol ether (Triton × 207), 3 Parts by weight of isotridecanol polyglycol ether (8 AeO) and 71 parts by weight of paraffinic mineral oil (Boiling range e.g. approx. 255 to over 377 ° C) mixes and in a friction ball mill to a fineness of less than 5 Micron grinded.

D. An emulsifiable concentrate is obtained from 15 Parts by weight of active ingredient, 75 parts by weight of cyclohexanone as a solvent and 10 parts by weight of ethoxylated Nonylphenol (10 AeO) as an emulsifier.

Chemical examples Example 1 2-Isocyanatosulfonyloxy-3-methyl-benzoic acid allyl ester

To a solution of 4.8 g (0.025 mol) of 3-methylsalicylic acid allyl ester in 25 ml abs. Toluene is added dropwise at 25 ° C Solution of 3.7 g (0.026 mol) of chlorosulfonyl isocyanate in 25 ml abs. Toluene. After dropping stops increasing the temperature is slowly increased to 110 ° C. and the mixture is heated for 6 hours Reflux. The mixture is cooled and the solvent is removed on Rotary evaporator. The remaining yellow oil (7.5 g 100% of theory) without further cleaning used.

Example 2 2- [3- (4-methoxy-6-methylpyrimidin-2-yl) ureidosulfonyloxy] - 3-methylbenzoic acid allyl ester

To 3.5 g (0.025 mol) of 2-amino-4-methoxy-6-methylpyrimidine in 15 ml of dichloromethane are dripped from a solution at 0 ° C 7.5 g (0.025 mol) of the product from Example 1 in 20 ml Dichloromethane. The mixture is allowed to come to room temperature and stirred 24 hours after. The reaction solution is mixed with 100 ml Diluted dichloromethane and with 50 ml of 1 N hydrochloric acid and Washed 50 ml of water. The organic phase is dried with sodium sulfate and removes the solvent on Rotary evaporator. The remaining viscous oil will crystallized by trituration with 1-chlorobutane. Man receives 7.4 g (68% of theory) of 2- [3- (4-methoxy-6-methylpyrimidin-2-yl) ureidosulfonyloxy] - 3-methylbenzoic acid allyl ester of mp. 127-128 ° C.  

Example 3 2- [3- (4,6-Dimethoxypyrimidin-2-yl) ureidosulfonyloxy] - 2-chloroethyl benzoate

2.02 g (0.013 mol) of 2-amino-4,6-dimethoxypyrimidine are in Dissolved 80 ml dichloromethane and at 0 ° C with 4.28 g (0.014 mol) 2-chloroethyl 2-isocyanatosulfonyloxy benzoate - dissolved in 20 ml dichloromethane - added. After stirring for 18 hours at room temperature Reaction mixture stirred in 600 ml of n-heptane. You get in this way 4.72 g (79% of theory) of 2- [3- (4,6-dimethoxypyrimidin-2-yl) ureidosulfonyloxy] - 2-chloroethyl benzoate, mp. 148-150 ° C.

Example 4 2- [3- (4,6-Dimethoxypyrimidin-2-yl) ureidosulfonyloxy] - allyl benzoate

1.55 g (0.01 mol) of 2-amino-4,6-dimethoxypyrimidine are in 100 ml dichloromethane dissolved and at 0 ° C with 3.40 g (0.012 mol) 2-Isocyanatosulfonyloxy-benzoic acid allyl ester - dissolved in 20 ml dichloromethane - added. To Stirring at room temperature for 18 hours is obtained by Aspirate 2.54 g (58% of theory) 2- [3- (4,6-Dimethoxypyrimidin- 2-yl) ureidosulfonyloxy] -benzoic acid allylester of Mp 110-112 ° C.

The following connections can be made on analog Create way.  

Tables 1a-c

Table 1a: (R²) _n = H; R³ = H

Table 1b: R³ = H

Table 1c

Table 2

Biological examples

The damage to the weed plants or the Crop tolerance was determined according to a key rated in which the effectiveness by value numbers of 0-5 is expressed. Here means:

0 = without effect
1 = 0-20% effect or damage
2 = 20-40% effect or damage
3 = 40-60% effect or damage
4 = 60-80% effect or damage
5 = 80-100% effect or damage

1. Pre-emergence weed action

Seeds or rhizome pieces of mono- and dicotyledons Weed plants were grown in sandy plastic pots Clay soil laid out and covered with earth. The in the form of wettable powders or emulsion concentrates Compounds according to the invention were then as aqueous Suspensions or emulsions with a water application rate from converted 600-800 l / ha in different Dosages applied to the surface of the earth.

After the treatment, the pots were in the greenhouse set up and under good growth conditions for the Weeds kept. The visual rating of the plant or the accidental damage occurred after the emergence of the Trial plants after a trial period of 3-4 weeks compared to untreated controls. As the Rating values in Table 2 show the Compounds according to the invention a good herbicidal Pre-emergence effectiveness against a wide range of Grasses and weeds.  

2. Post-emergence weed action

Seeds or rhizome pieces of mono- and dicotyledon weeds were laid out in plastic pots in sandy clay soil, covered with earth and in the greenhouse under good Growth conditions attracted. Three weeks after the The test plants were sown at the three-leaf stage treated.

The as wettable powder or as emulsion concentrates formulated compounds according to the invention were in different doses with a water application rate of converted 600-800 l / ha on the green parts of the plant sprayed and after about 3-4 weeks of standing Trial plants in the greenhouse under optimal Growth conditions the effect of the preparations optically in Rating compared to untreated controls.

The agents according to the invention also have post-emergence good herbicidal activity against a broad spectrum economically important grasses and weeds (Table 3).

3. Crop tolerance

In further experiments in the greenhouse, seeds of one larger number of crops and weeds in sandy clay soil laid out and covered with earth.

Part of the pots were immediately as described under 1. treated, the rest in the greenhouse until the Plants had developed two to three real leaves and then with the substances according to the invention in different dosages, as described under 2., sprayed.  

Four to five weeks after application and standing in Greenhouse was determined by means of an optical rating, that the compounds according to the invention have two cotyledons Cultures such as B. soybeans, cotton, rapeseed, sugar beet and Pre-and post-emergence potatoes themselves high dosage of active ingredient undamaged. Some Substances also protect Gramineae crops such as B. barley, wheat, rye, sorghum, millet or Rice. The compounds of formula I thus have a high Selectivity when used to combat undesirable Plant growth in agricultural crops.

Table 2

Pre-emergence effect of the compounds according to the invention

Table 3

Follow-up effect of the compounds according to the invention

Claims (9)

1. Compounds of formula I or their salts wherein
R¹ (C₁-C₈) alkyl which is substituted one or more times by halogen or once or twice by (C₁-C₄) alkoxy; (C₂-C₈) alkenyl, (C₂-C₈) alkynyl, both of which can optionally be substituted one or more times by halogen or once or twice by (C₁-C₄) alkoxy,
R² independently of one another halogen; Nitro; (C₁-C₄) alkyl or (C₁-C₄) alkoxy, both of which may optionally be substituted one or more times by halogen,
R³ is hydrogen; (C₁-C₈) alkyl; (C₂-C₈) alkenyl or (C₂-C₈) alkynyl,
R⁴ is a heterocyclic radical of the formulas where E = CH or N,
n 0, 1, 2 or 3,
R⁵, R⁶ independently of one another hydrogen; Halogen; (C₁-C₄) alkyl or (C₁-C₄) alkoxy, both of which may optionally be halogenated one or more times; Di- (C₁-C₄) alkoxy- (C₁-C₂) alkyl; Cyclopropyl, -OCHR⁸COOR⁹; -NR⁹R¹⁰ or (C₁-C₄) alkylthio,
R⁷ (C₁-C₄) alkyl,
R⁸ is hydrogen or (C₁-C₄) alkyl and
R⁹, R¹⁰ independently of one another hydrogen; (C₁-C₄) alkyl; (C₂-C₄) alkenyl or (C₂-C₄) alkynyl
mean. 2. Compounds of formula I of claim 1 and their salts, wherein in formula I R¹ (C₁-C₄) alkyl which is substituted as described in claim 1, or (C₃-C₄) alkenyl as described in claim 1 can be substituted; R² is halogen, (C₁-C₃) alkyl or (C₁-C₃) alkoxy, which may be substituted as described in claim 1; n = 0, 1 or 2; R³ is hydrogen, (C₁-C₄) alkyl or allyl; R⁴ is a residue of the formula and R⁵ and R⁶ independently of one another are halogen, (C₁-C₄) alkyl or (C₁-C₄) alkoxy, both of which can be substituted by halogen. 3. Compounds of formula I of claims 1 and 2 and their salts, wherein R¹ (C₁-C₄) alkyl which is substituted as described in claim 1, or (C₃-C₄) alkenyl which is substituted as described in claim 1 can be; n = 0; R³ is hydrogen, R⁴ is a radical of the formula and R⁵ and R⁶ independently of one another are chlorine, bromine, (C₁-C₄) alkyl, (C₁-C₄) alkoxy, OCF₂H, OCH₂CF₃ or CF₃. 4. A process for the preparation of the compounds of formula I according to claims 1 to 3, characterized in that

• (a) a compound of formula (II) with a compound of formula (III) implements, or
• (b) a compound of formula (IV) with a chlorosulfonylurea of the formula (V) implements, or
• (c) a substituted benzoic acid of the formula (VI) with an alkylating reagent of the formula (VII) R¹-X (VII) where X is a nucleofugic leaving group such as. B. halogen, alkyl-SO₂-O- or tosyl is implemented.

5. Herbicidal agents, characterized in that they have a Compound of formula I of claims 1 to 3 or whose salts contain, in addition to inert carriers. 6. Plant growth regulating agents, thereby characterized in that it is a compound of formula I of Claims 1 to 3 or their salts in addition to inert Contain carriers. 7. Use of compounds of formula I according to Claims 1 to 3 as herbicides or Plant growth regulators. 8. methods of controlling undesirable plants, characterized in that one on this or their Cultivated areas an effective amount of a compound of Formula I of claims 1 to 3 applied. 9. Process for regulating the growth of plants, thereby characterized that one on this or the acreage an effective amount of a compound of formula I of Claims 1 to 3 applied.