HU197173B - Herbicides comprising sulfamoyl-urea derivatives as active ingredient and process for producing the active ingredients - Google Patents

Abstract

The invention relates to herbicidally active sulfamoyl urea derivatives, including herbicidal formulations and uses thereof to control the growth of noxious plants, i.e., weeds.

Description

FIELD OF THE INVENTION The present invention relates to a herbicidal composition containing a sulfamoylurea compound of formula (I) as an active ingredient, and to a process for its preparation.

British Patent 2113217A and Japanese Patent 5,815,962 disclose sulfamoyl urea-containing herbicides, but where the active ingredient, in particular the phenyl substituents, differs from the present invention.

The active ingredient of the composition of the present invention is a compound of formula (I) wherein

Z is N;

R ¹ is C 1 -C 4 alkyl;

R ² is C 1-4 alkoxy;

^R5 is an (a) group of formula, wherein

R ^T is a moiety of formula (b) or a moiety of formula (c) wherein

R @ 4 is C1 -C3 alkyl; R @ 4 and R @ ¹⁰ are C1 -C4 alkyl;

R ¹¹ is C 1-3 alkyl.

Compounds of formula (I) may be prepared by reacting an appropriately substituted aminotriazine of formula (IV), wherein R ¹ , R ² and Z are as defined above, with a halosulfonyl of formula OCN-SO 2 -Hal isocyanate, wherein Hal is halogen, such as chlorine, fluorine or bromine, to give a halosulfonylurea of formula (II).

Compound is then reacted with the acid halide in the presence of at least a stoichiometric amount of a suitably substituted (III) amine of formula is obtained (II) - are reacted to give the compounds of the invention of formula (I). - wherein ^R5 is as defined above

The following examples are intended to further illustrate the invention without, however, limiting its scope.

Example 1 Preparation of 1- [2- (1,1-dimethoxyethyl) phenylsulfamoyl] -3- (4-methyl, 6-methoxy-1,3,5-triazin-2-yl) urea

(a) Weigh 6.5 g of ortho-nitroacetophenone, 6.0 g of trimethyl orthoformate, 0.25 g of p-toluenesulfonic acid and 50 ml of methanol. The stirred reaction mixture was heated to 60 ° C and maintained under a nitrogen atmosphere. After thermostating at 60 ° C for 3 days, HPLC showed that the reaction was 90 percent complete. The reaction mixture was cooled, poured into aqueous sodium carbonate solution, the solvent removed and extracted with methylene chloride. The organic phase was dried over sodium carbonate and the solvent was removed again. The residue was dissolved in methanol (0.5 g) containing sodium carbonate, transferred to a Parr shake flask and reduced to 5% palladium on activated carbon. The hydrogenated reaction mixture is then filtered to remove the catalyst. Most of the methanol was evaporated and the residue was extracted with methylene chloride. After phase separation, the organic phase was dried over anhydrous sodium carbonate and the solvent was evaporated to give a clear oil, which was found to be 2- (1,1-dimethoxyethyl) aniline by NMR analysis.

b) 50 ml of methylene chloride was kept in an ice bath at 0-5 ° C followed by 1.38 g of 4-methyl-6-methoxy-2-amino-1,3,5-triazine and 1.60 g of chlorosulphonyl. isocyanate is added. After stirring for 3 hours at ice temperature, a solution of triethylamine (1.1 g) and methylene chloride (1.70 g) in the present example (a) was added.

The reaction mixture is then allowed to warm to room temperature and washed three times with ice-cold water and dried over anhydrous sodium sulfate. Filtration followed by removal of the solvent gave a paste which was dissolved in 80 ml of diethyl ether. The ether insoluble residue was removed, the ether evaporated and the resulting solid residue was taken up in pentane and filtered. After drying under reduced pressure, 1.3 g of a yellow crystalline solid are obtained, which according to NMR analysis gives the title compound, 1- [2- (1,1-dimethoxyethyl) phenylsulfamoyl] -3- (4- methyl-6-methoxy-l, 3,5-triazin-2-yl) urea.

1 H NMR (d, CDCl 5): 1.75 (s, 3H); 2.55 (s, 3H);

4.05 (s, 3H); 3.8-4.2 (m. 4H); 6.8-7.7 (m,

4H); 8.3 (bs, 1H); 9.7 (wide s,

IH); 12.4 (broad s, 1H).

Example 2 1- [2- (2-Methyl-1,3-dioxolan-2-yl) phenylsulfamoyl] -3- (4-methyl-6-methoxy-1,3,5-triazine-2- il) urea

(a) Add 10 g of ortho-nitroacetophenone, 40 ml of ethylene glycol and 0.5 p-toluenesulfonic acid to a round bottom flask.

The stirred mixture was then heated to 140 ° C and sparged with nitrogen gas. After about 36 hours, HPLC showed 90 percent complete. The reaction mixture was cooled, filtered and the solid was washed with aqueous sodium carbonate and dried to give 8 g of a white crystalline solid. The material was then taken up in methanol and aqueous sodium carbonate solution, transferred to a Parr shake flask, and 0.5 g of palladium on carbon was added. The reaction mixture was hydrogenated at 50 psi for 2 hours until hydrogen uptake was complete. The hydrogenated mixture was then removed by filtration and the solvent was evaporated on a rotary evaporator. The residue was then extracted with a mixture of water and methylene chloride.

After phase separation, the organic phase is dried over anhydrous sodium sulfate and evaporated on a rotary evaporator to give 7.0 g of a clear oil (which solidifies on standing), 2- (1,3-dioxolan-2-ylmethyl) by NMR analysis. )aniline.

b) To 150 ml of methylene chloride in an ice bath at 0-5 ° C, 1.41 g (0.01 mol) of 4-methyl-6-methoxy-2-amino-1,3,5-triazine and 1.54 g of chlorosulfonyl isocyanate is added. The reaction mixture is stirred at ice temperature until all solids have dissolved and a solution of methylene chloride (0.01 mol) in triethylamine (0.01 mol) and in amine (0.01 mol) in the present example is added dropwise over 1.5 hours. The reaction mixture was allowed to warm to room temperature, then cooled in an ice bath and poured into 2% aqueous hydrochloric acid, whereupon phase separation followed by shaking. The organic layer was washed three times with ice-cold water and dried over anhydrous sodium sulfate. Removal of the solvent gave a paste which was crystallized by the addition of a small amount of diethyl ether. After filtration, 2.6 g of 1- (2- (2-methyl-1,3-dioxolan-2-yl) phenylsulfamoyl) -3- (4-methyl-6-methoxy-1,3,5- triazin-2-yl) urea.

1 H NMR (d, CDCl 3): 1.6 (s, 3H); 2.55 (s, 3H);

3.25 (s, 6H); 4.0 (s, 3H); 6.9-9.7 (m,

4H); 8.4 (wide s, 1H>; 9.7 (wide s,

IH); 12.2 (broad s, 1H).

Non-exemplary compounds of the compounds of formula I can be prepared by one skilled in the art by varying the starting materials using the same techniques.

For the control of weeds, a composition comprising an effective amount of the compounds of the invention is applied to the soil or to the surface of plants grown from the soil prior to weed growth.

Of course, the formulations of the invention include brushing a mixture of lozenges.

The term "effective amount" refers to the amount of the compounds of the invention that eradicate weeds, rendering the weeds unfit for growth in space, while the valuable plants between the weeds do not suffer damage.

The amount of the compounds of the invention which exhibit satisfactory herbicidal activity may vary widely and will depend upon a number of factors such as, for example, the type of weed, the degree of weed proliferation, the climatic conditions, the condition of the soil and the method of treatment.

Usually, the treatment is carried out with a composition containing 1.1 kg / ha or less of active ingredient, although in many cases 5.5 kg or more of active ingredient is needed per hectare.

The efficacy of a given compound against a particular species of weed can, of course, be readily determined in routine laboratory conditions or in field experiments known per se. It is preferred that the treatment is carried out with a composition according to the invention containing from 0.01 to 2.2 kg of active ingredient per hectare.

The compounds of this invention may be formulated into preparations by routine methods using known and commonly used herbicidal carriers and adjuvants.

The herbicidal compositions according to the present invention contain from 5 to 95% by weight of the sulfamoylurea active ingredient of the formula (I), with a suitable carrier or carrier such as acetone, water, clay, talc, diatomaceous earth and optionally additives such as dispersants, wetting agents or surfactants. such as Tween 20.

Preferred compositions are wetting powders, soluble powders, dispersible granules, or aqueous emulsion concentrates which may be diluted with water at the point of use.

A very useful formulation of the invention is a wettable powder containing 85% by weight of the active ingredient of Examples 1 or 2, 10% by weight of attapulgite clay carrier and 5% by weight of N-methyl-N-allylturate Na salt wetting agent.

In order to achieve a broader spectrum of action, the compositions of the invention may, if desired, also be used in admixture with other herbicides.

Preferred herbicides which can be combined with the formulations containing the active ingredient of the formula I are atrazine, hexazinone, metribuzin, amethryn, cyanazine, cyprazine, promethone, prometryn, propazine, simazine, terbutryn, propham, alachlor. , acifluorfen, bentazone, metolachlor and az, Ν-dialkylthiocarbamates such as EPTC, butylate or vernolate.

The above herbicides and other herbicides such as those described in the Fibericide Handbook of the Weed Science Society of America may optionally be combined with the compositions of the invention.

Application of the herbicidal compositions can be carried out by known methods, usually by spraying it in the form of an aqueous spray. Such applications can be accomplished by conventional devices, optionally air sprays. The soil application is incorporated into the soil by natural leaching, rain or melted snow. However, if desired, the herbicides may be applied to the soil by conventional tillage.

The compositions of the present invention are effective in controlling broadleaf and grass weeds, whether pre-emergence or post-emergence. Suitable for example are annual plants such as Brush Lawn, Fescue, White Mustard, Cress, Italian Dairy, Dried Grass, Star String, Wild Barley, Downy Silk, Cocksfoot, Mallard, Fenugreek, Hemp, dawn, frog duck, ryegrass, snapper and similar perennial grasses and weeds, as well as biennial plants such as sandy gooseberry, burdock, papaya and perennials such as kale, Johnson grass, Canadian thistle, horseradish, dandelion, horsetail, borage, sceria, gorse and the like.

The herbicidal activity of the compositions of the invention before and after emergence was tested under controlled laboratory conditions (light, temperature and humidity) by spraying different varieties of broadleaf and grass weeds with the composition. The degree of herbicidal activity was evaluated (periodically after treatment) and a numerical damage ratio (NIT) from 0 (no damage) to 10 (all plants killed) was given. The following table shows the NIR for each weed species (commonly known) as 1 molar equivalent of the active ingredient prepared in Example 1 and the aqueous / acetone formulation containing Tween 20 21 days after (pre- and post-emergence) treatment. The application rate was 0.55 kg per hectare.

weeds hatching pre- treatment hatching post treatment Teagyom 9 5 Jimson-weed 9 10 White mustard 9 10 Yellow sclera 10 6 Yellow Brush Lawn 10 8 Big toad 9 - Johnson grass 9 8 senna 9 8 Fluffy silk sweater 9 8 High dawn 9 3 wild oats 8 3 Barnyardgrass 9 4

The following table shows the NIR values for the formulations containing the active ingredient prepared according to the procedure of Example 2, 22 days after (pre- and post-emergence) treatment. The application rates were 0.55 and 1.1 kg per hectare.

weeds hatching pre- treatment hatching post treatment

0:55 1.1 0.55 1.1 Teagyom 6 6 5 5 Jimson-weed 5 6 8 8 White mustard 8 8 8 10 Yellow sclera 10 10 6 7 Yellow Brush Lawn 7 8 6 7 Big toad 7 8 - - Johnson grass 7 8 6 6 senna 3 6 6 6 Fluffy silk sweater 5 5 8 8 High dawn 4 5 5 6 wild oats 8 7 2 1 Barnyardgrass 8 8 3 5

Although the invention has been described in sufficient detail above, it will be appreciated that more variations may be accomplished by the ordinary skilled person without going beyond the scope of the claimed scope.

Claims (6)

PATENT CLAIMS CLAIMS 1. A herbicidal composition comprising 5-95 tX of the compound of formula (I) as an active ingredient. Z is N; R ¹ is C 1 -C 4 alkyl; R ² is C 1-4 alkoxy; R ⁵ is a group of formula (a) wherein: R ⁷ is a group of formula (b) or (c) wherein R ⁸ is C 1 -C 3 alkyl, R ⁹ and R ¹⁰ are C 1 -C 4 alkyl; R ¹¹ is C 1-3 alkyl; and / or an agriculturally acceptable carrier or diluent, preferably water, acetone or substance, and optionally an additive, preferably a dispersing or wetting agent. Priority: 12.12.1985. 2. A herbicidal composition, wherein the active ingredient is 5-95 tX of a compound of formula I wherein Z is N; R ¹ is C 1 -C 4 alkyl; R ² is C 1-4 alkoxy; ^R5 is (a) a group of formula wherein: R ⁷ is a group of formula (b) wherein R ^s is C 1 -C 3 alkyl; R ⁹ and R ¹⁰ are C 1 -C 4 alkyl; and an agriculturally acceptable carrier or diluent, preferably water, acetone or clay, and optionally an additive, preferably a dispersing or wetting agent. Priority: 04/02/85. 3. A herbicidal composition, wherein the active ingredient is from 5 to 95% by weight of the compound of formula (I) Z is N; R ¹ is C 1 -C 4 alkyl; R ² is C 1-4 alkoxy; ^R5 is (a) a group of formula 20 wherein: R ⁷ is a group of formula (c) wherein R ¹¹ is C 1 -C 3 alkyl and contains an agriculturally acceptable carrier or diluent, preferably water, acetone or substance, and optionally an additive, preferably a dispersing or wetting agent. 30 priority; 03/12/1984. Composition according to claim 3, characterized in that the active ingredient is 1- [2- ⁽ T2-methyl-1,3-dioxolan-2-yl) phenylsulfamoyl] -3- (4-methyl-6-methoxy) -1,3,5-triazin-2-yl) urea. Priority: 12.12.1984. Composition according to claim 2, characterized in that the active ingredient is 1- [2- (1,1-dimethoxyethyl) phenylsulfamoyl] -3- (4-methyl-6-methoxy-1,3, Contains 5-triazin-2-yl) urea. Priority: 04/02/85 6. A process for the preparation of a compound of formula I wherein: Z is N; R ¹ is C 1 -C 4 alkyl; R ² is C 1-4 alkoxy; R ⁵ is a ceopor of formula (a) wherein R ⁷ is a group of formula (b) or (c) wherein R ⁸ is C 1 -C 3 alkyl, Π ⁹ and R ¹⁰ are alkyl; R ¹¹ is 1-3 kilo, characterized in that at least a stoichiometric amount of a halosulfonylurea of formula II, wherein Hal is halogen, R ¹ , R ² and Z are as defined above, substituted amine - wherein ^R5 is as defined above - are reacted.