CS239916B2 - Herbicide agent - Google Patents

Abstract

Novel tri-mixed alkylsulfonium salts of N-phosphonomethylgly-cine are disclosed herein, having the formula < IMG > in which R1, R2, are R3 represent C1-C6 alkyl and n is zero or one, wherein no more than two of R1, R2, or R3 are identical. The compounds are useful in regulating the natural growth or development of plants and as herbicides.

Description

BACKGROUND OF THE INVENTION The present invention relates to a composition for regulating natural plant growth or plant development or herbicidal activity which contains, as an active ingredient, the trialkyl ammonium salt of N-lyricin [nerynglycine] The composition can be used in agriculture and horticulture to promote various plant properties ·

It is well known to workers in agriculture and horticulture that the various characteristics of plant growth can be mooified or controlled to achieve favorable results.

For example, in certain types of treatments, delolization of plants can be achieved, for example, by preventing further development of the leaves while at the same time preventing further development of the productive parts of the plants. the following harvesting is facilitated · DeH lants are particularly suitable for growing flax, cotton, beans and other crops of a similar nature · However, deloliation of the leaves leaves no herbicidal action as other parts of the plant are undamaged · Plant destruction is also undesirable, when only deloliation is to take place, as Rossi's and the dead keep the leaves. ,

Another response of plants to growth regulators is the general retardation of vegetative growth · This response has various beneficial consequences · Certain plants reduce or eliminate the normal tip ending, the main stem is shorter and side branching ·

This change in natural growth or development leads to smaller, denser growths, which often find larger in dry conditions and for 1-year action by pests!

If the rate of vertical growth of such grasses is slowed, the development of roots is encouraged and a denser, firmer grass is developed. · Slowing the growth of turf grasses also extends the mowing interval of lawns, gollies and similar grassy areas.

For many types of plants, such as silage plants, potatoes, sugar beets, sugar cane, grapes, melons and fruit trees, slowing of vegetative growth leads to an increase in carbohydrate content in plants at harvest.

It is believed that slowing or suppressing such growth at a suitable stage of plant development causes less available carbohydrates to be consumed for vegetative growth, and thus the starch and / or sucrose content of the plant is reduced. fruit stoom growth results in shortening of branches and greater fullness of shape and often leads to less vertical growth · These facts support the ease of access to the orchard and facilitate fruit harvesting ·

The novel compositions for regulating the natural growth and development of plants having a herbicidal action, if appropriate, contain, as an active substance, the novel triaclyl 3-olio () salts of the N-lsloirmerylglycine of the formula I

R ³

I and ² -se

(i) wherein R ^1, R ² and R j are each an alkyl group having 1 to 6 carbon atoms, where at most two of these groups · 'are identical ·

The composition according to the invention is used in an effective amount which affects the growth of the plant but does not destroy the plant. However, it can also be used in an amount chosen to deliberately destroy unwanted vegetation in the post-emergence state.

The term "natural plant growth and development" refers here to the normal life cycle of a plant in accordance with its genetics and the 8 means where it grows, without the effects of artificial outdoor influences. Preferably, the composition of the invention is used to increase the sugar content of sugar beet and sorghum grown in fields. By "affecting or regulating" is meant here any temporary or permanent modifications induced by the action of chemicals, or any deviation from the normal cycle of the plant, leading to a shortening of the life cycle or destruction of the plant.

By herbicidally effective amount is meant herein any amount of the composition of the invention that destroys or destroys a plant. By "plant" is meant germinated seeds, emerging seedlings or the plant itself including roots and aerial parts. The herbicidal action includes destroying the plant, defoliating, drying the plant development, burning the leaves and stunting the plant. Herbicidal action is generally obtained at higher rates of application than by deliberately influencing plant growth.

The term "alkyl" refers to a straight or branched chain alkyl group. The number of carbon atoms is always meant including the lower and upper indicated limits. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, butyl, n-butyl, sec-butyl, pentyl, isopentyl, neopentyl, sec-pentyl, hexyl, isohexyl, sec-hexyl and the like groups. The sulfonium cation always has three alkyl moieties, but no more than two of these plural moieties are the same.

Specific examples of the active compounds according to the invention of formula I include diethyl methylsulfonium salt of N-phosphonomethylglycine, dimethylethylsulfonium salt of N-phosphonomethylglycine, diethylisopropylsulfonium salt of N-phosphonomethylglycine, diethyl-n-butylsulfonium salt of N-phosphonomethylglycine, dimethyl-n-butylsulfonium salt of N-phosphonomethylglycine and dimethylisopropylsulfonium salt of N-phosphonomethylglycine.

According to the invention, the control of the natural growth or development of plants is achieved by direct application of the composition of the invention containing the compound of formula I as an active ingredient to plants or any aboveground part thereof approximately 4 to 10 weeks prior to harvesting. herbicidal effect

The amount of composition according to the invention which can be said to be effective depends not only on the treatment material chosen, but also on the desired effect, the type of plant and its state of development and whether permanent or transient phenomena are to be achieved. Other factors that influence the determination of a suitable effective amount for controlling plant growth are the method of application and weather conditions such as temperature or precipitation. The regulatory action may depend on the action of the active substance either on the physiological processes or on the morphology of the plants, or both together or sequentially. Morphological changes are generally observable by changes in size, shape, color or texture of the treated plant or any part thereof, flowers or fruits produced.

AND

Changes in the process of the processes take place in the treated plant and are usually hidden from the eye of the observer. Three such types take place in the production, placement, storage or utilization of naturally occurring chemical chemicals in the plant, such as hormones. Physiological changes in aphids may be visually detectable if accompanied by changes in mmrfOlogircKýix · In addition, numerous analytical methods are known to determine the nature and extent of changes induced by various physiological processes.

Thus, the composition of the invention is used to control the natural growth of plants or the development of treated plants in a number of different ways, with each active ingredient not necessarily having the same regulatory effect on each type of plant being treated or at each dosage. As mentioned above, the response of the plant varies depending on the active agent used, its dose, the species of plant and other factors mentioned above.

The herbicidal action is achieved in a similar manner and the amount of active ingredient used varies according to the desired effects.

The active compounds of the formula I are readily prepared from N-phosphonomeeylyglycine by reacting it with silver oxide to form a silver salt or with sodium hydroxide to form the sodium salt and then treating the silver or sodium salt with triacidone phosphonium and halogenide or triacetone sulfoxone. Alternatively, the glycine may be reacted directly with a trialkylsulfoneimide halide in the presence of propylene oxide. N-phosphine glycine is generally available under the trade name glyphosate.

It can be prepared by phosphonomeethylation of glycine, by reaction of ethyl acetate with formaldehyde and with ethylphosphite, or by oxidation of N-phosphonimethylglycine. Such methods are described in U.S. Pat. No. 3,799,758 (Franz, Mar. 26, 1974).

As exemplified by the following examples, the compositions of the invention may either control the induced growth or development of plants or may control weeds. While the regulatory response is often desirable in the true sense of the word, influencing the harvest economy is very often of paramount importance. Therefore, the increase in yield, individual plants, increase in yield per unit area, and the reduction of the cost of harvesting and / or further processing of plants are always considered to determine the individual regulatory effect of the composition of the invention on plant growth or development.

When used in a composition according to the invention as a growth regulator or as a herbicide, it is most convenient to apply them directly to the plant after it has emerged. In agricultural applications, the compositions according to the invention contain, in addition to the active ingredient, excipients and carriers to facilitate their dispersion. Examples of ingredients or carriers include water, organic solvents, powders, granules, surfactants, water-in-oil and oil-in-water emulsions, lubricants, dispersants and emulsifiers. The composition according to the invention is generally in the form of a powder, a solution, a emulsifiable coceenate or a reconstituted powder.

A. Pills

The powders are a dense powdered network comprising the active compound of the formula I and a free-flowing solid carrier. They are intended for use in dry form, quickly settle on plants, and are not carried by wind to networks where their presence is undesirable.

The carriers may be of vegetable or mineral origin and are preferably organic or inorganic powders having a high bulk density, poor surface area and low capsule absorption capacity. Suitable carriers include mica talc, sachets, kaolin clays, tobacco powder and ground calcium phosphate rock.

Powder properties are sometimes improved by incorporating a liquid or solid wetting agent of ionic, anionic or nonionic character. Preferred wetting agents include alkylbenzenesulfonates and alkylnaphthalenesulfonates, sulfated fatty alcohols, acid amides or amines, long chain sodium isothionate esters, sodium sulfosuccinate esters, sulfated or sulfonated fatty acid esters, petrolsulfonates, sulfonated acetylenes and di-etheric oils.

Dispersants are also used in some powder blends. Typical dispersing agents include methylcellulose, polyvinyl alcohol, lignin sulfonates, polymeric alkyl naphthalenesulfonates, sodium naphthalenesulfonate, polymethylene bisnaphthalenesulfonate and sodium long-chain N-methyl-N-taurates.

In addition, powder compositions often contain absorbent grinding aids to facilitate powder manufacture. Suitable grinding aids are attapulgite clay, diatomaceous earth silica, synthetic fine silica and synthetic calcium and magnesium silicates.

A typical powder composition comprises the carrier in an amount of 30 to 90% by weight of the powder as a whole. The grinding aid comprises from 5 to 50% by weight and a surfactant up to about 1.0% by weight. Optionally, the dispersant comprises about 0.5% by weight and may also contain minor amounts of anticaking and antistatic agents. The particle size of the mixture is generally 30 to 50 microns.

B. Solutions

Aqueous solutions of the active compound of the formula I are prepared in such a way that 9 to 1975 liters per hectare contain the required amount of active compound. A small amount of non-phytotoxic surfactant, typically 0.05 to 0.5% by weight, is generally incorporated into the solution to improve the ability of the solution to wet the surface of the plant and thereby better distribute on the surface of the plant. Anionic, cationic and nonionic and ampholytic surfactants are useful in this regard.

Suitable anionic surfactants include alkali metal salts, ammonium salts and amine salts of fatty alcohol sulfates having from 8 to 18 carbon atoms in the fatty chain and sodium salts of alkylbenzenesulfonates having from 9 to 15 carbon atoms in the alkyl chain or ^r. Suitable cationic surfactants include dimethyldialkylquaternary ammonium halides having an alkyl chain of 8 to 18 carbon atoms. Suitable anionic surfactants include polyoxyethylene adducts of C 10 -C 18 fatty alcohols, polyethylene oxide condensates of C 6 -C 12 alkyl chain and 5 to 25 moles of ethylene oxide condensed per mole of alkyl phenol with 10 to 40 sorbitan ester polyethylene oxide condensates moles of ethylene oxide condensed per mole of sorbitan ester.

Suitable ampholytic surfactants include secondary and tertiary aliphatic amine derivatives having one aliphatic substituent containing 8 to 18 carbon atoms and another substituent containing an anionic, water-solubilizing group, such as a sulfate or sulfonate group. Examples include sodium-3-dodecylaminopropionate. and sodium 3-dodecylaminopropanesulfonate. Suitable zwitterionic surfactants include derivatives of aliphatic quaternary ammonium compounds with one aliphatic substituent containing 8 to 18 carbon atoms and another substituent containing an anionic, water-solubilizing group. Examples are 3- (N, N-dimethyl-N-hexadecylammonio) propane-1-sulfonate and 3- (N, N-dimethyl-N-hexadecylammonio) -2-hydroxypropane-1-sulfonate.

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jKiiulg yvtelnó кг..r · ^ c ».. η t rálv if _{(vJ.Icwatelíié} chickens .. · cntráV / are concentrates in which the active ingredient of formula .II oi.'iu.lga» ini fronto-dec dissolved In a water-immiscible solvent Prior to use, the concentrates are diluted with water to form a suspended emulsion of solvent droplets.

Typical solvents for emulsifiable concentrates include vegetable oils, chlorinated non-water-miscible wipes, non-water-miscible esters and ketones. ‘

Typical emulsifying agents are anionic or nonionic surfactants or mixtures thereof. Examples are long chain mercapto -polyethoxyalcohols, alkylarylpolyethoxyalcohols, sorbitol fatty acid esters, polyoxyethylene ethers with sucrated fatty acid esters, polyoxyethylethyl glycol esters with fatty acids or with rosin acids, fatty alcohol and ammonium sulfonate fatty acid sulfates, calcium sulfates in oil or preferably mixtures of the above emulsifying agents. Such emulsifiers generally comprise from 1 to 10% by weight of the composition as a whole.

Typical emulsifiable concentrates contain from about 15% to about 50% by weight of the active ingredient of the formula (1), from about 40% to about 82% of the solvent, from about 1% to about 10% of the emulsifier. They may also contain other additives, such as flow aid and adhesion promoter.

D. Wettable powders

Wettable powders are water dispersible mixtures containing the active compound of the formula I, an inert solid non-builder and one or more surfactants to achieve rapid wetting and to prevent flocculation when suspended in water.

Suitable solid extenders are both natural minerals and materials synthetically derived from such minerals. Examples include kaolinity, attapulgite clay, mottmorillonite clays, synthetic silica, synthetic magnesium silicate, and calcium sulfate dihydrate.

Suitable surfactants include nonionic and antontonic agents which act as wetting and dispersing agents. Typically both wetting and dispersing agents are included. Preferred wetting agents include alkylbenzenesulfonates and alkylnaphthalenesulfonates, sulfated fatty alcohols, amines or acid amides, long chain esters of taerium isothiate, sodium sulfojatearate esters, sulfated or sulfonated fatty acid esters, peerolsulfothealene, sulfonated vegetable oils and sulfonated vegetable oils. Preferred dispersing agents are methylcellulose, polyvinyl alcohol, lignin sulfonates, polymeric alkyl and N- and 4-sulfonates, sodium naphthalene sulfotate, polymethylenebistaphthalene sulfotate and long-chain N-methyl-N-taurate acid.

Typical wettable powders contain 25 to 90% by weight of the active compound of the formula I, 0.5 to 2.0 lb of a wetting agent, 0.25 to 5.0% of a dispersant and 9.25 to 74.25% of an inert extender. often 0.1 to 1.0% of the extender is replaced by a corrosion inhibitor and / or antifoam.

E. Methods of Use

In general, any post-emergence deposition method can be used for use, including the use of conventional dusting or spraying equipment. The amount of active compound of the formula I required to obtain a herbicidal or regulatory effect depends on the nature of the plant species to be treated and on the existing conditions. The herbicidal effect is generally obtained when the active compound is used in an amount of 0.112 to 56 kg / ha, preferably at a rate of 1.12 to 11.2 kg / ha, while the control of plant growth is generally achieved by using the active compound in a plurality of quantities. 0.112 kg / ha and 22 kg / ha and preferably 0.56 to 5.6 kg / ha. It will be appreciated by those skilled in the art that lower-potency substances must be used in greater quantities than higher-potency substances to achieve the same degree of control.

He did

Di-n-butylmethylsulphonium salt of N-fluoromethylglycine

50 ml of water, 5.1 g (0.03 mooy) of N-phosphonomerylglycine, and

8.65 g (0.03 mooy) of di-n-butylethylsulfonamide. 2.2 g (0.037 mole) of propylene oxide are additionally introduced into the vessel. The reaction mixture as a whole is left to stand overnight at room temperature. At the end of this time, the reaction mixture is extracted three times with diethyl ether and the phases are separated. The aqueous phase is stripped off to give 11.1 g of product. This product is triturated with tetramethylsilyl. The mixture was triturated with 20 ml of acetone and then with 10 ml of diethyl ether and extracted to give a solid. The melting point of this product is confirmed by proton nuclear msagintic resonance, which indicates that it is the N-flthyltylsulphonium salt of N-flsylmethylglycine.

Example 2

N-phosphinolyl glycine diethyl ethyl sulfonate

In a similar manner to that described in Example 1, 50 ml of water, 6.76 g (0.04 mooy) of N-phosphonomeeyl glycine, 9.3 g (0.04 mooy) of dirtylmethylthioylumide, and 2.9 g (0.05 moou) of of propylene oxide was allowed to react overnight at room temperature, extracted three times with water and the aqueous phase was stripped of volatiles to give 12.3 g of product. After trituration with acetone and dirtylereree and stripping off the volatiles, 12.0 g of N-phosphonylmerglycine diethylmethylsulphonium salt (decomposition at 60 to 65 ° C) is obtained. Molecular structure of the product was confirmed by proton nuclear magnetic resonance, suggesting that it is the compound being prepared.

Example 3

N-phosphinylmethyl-glycine dimethyl salt

In a similar manner to that described in Example I, 50 ml of water, 6.76 g (0.04 mooy) of N-phosphonorneeyyglycine, 9.3 g (0.04 mooy) of dimethylisopropylsulfonium, and 3.5 g (0) of water. The 0.1 mol / propylene oxide was allowed to react overnight at room temperature, extracted twice with diethyl ether and the aqueous phase was stripped off to give 11.8 g of product. After trižulOiání acetone / 10 twice modes odeiene product, the artery and vein to obtain 11.2 g of product he ^p ° 3 ^{1.52 second} The proton neutral magnetic resonance after curing the molecular structure of the product, such as the dieyl propyl pyrophenyl salt of N &apos;

Example 4

N-phosphonomethylglycine dimethyl-n-butylsulfonium salt

In a similar manner as described in Example 1, 50 mL of water, 6.8 g (0.04 mol) of N-phosphonomethylglycine, 10.0 g (0.04 mol) of dimethyl-n-butylsulfonium iodide and 3.5 g / 0 1.0 mol / propylene oxide was allowed to react overnight at room temperature, extracted twice with diethyl ether, the phases were separated and the volatiles were stripped off to give 12.4 g of product. After trituration with acetone (twice with 10 ml each of acetone) and stripping off, 12.9 g of a hygroscopic white solid is obtained. The molecular structure as the dimethyl-n-butylsulfonium salt of N-phosphonomethylglycine was confirmed by proton magnetic resonance.

Other active compounds of the formula I can be prepared according to the above-mentioned processes from suitable starting materials.

Example 5

This example illustrates the herbicidal activity of a composition according to the invention comprising as active ingredient compounds prepared according to the above examples. The efficacy of the composition according to the invention after emergence is demonstrated.

15.2 x 22.9 x 8.9 cm aluminum bowls are filled to a depth of 7.6 cm with sandy loose soil containing 50 ppm each of the commercial fungicide cis-N (trichloromethyl) thio] -4-cyclohexene-1, 2-dicarboximide (Coptan) and fertilizer 17 17-17 (17% by weight nitrogen, 17% phosphorus pentoxide and 17% potassium oxide). Rows are squeezed across each bowl and the seeds of broadleaf weeds and grasses are sown, each in a single row. The effect on the following plants shall be examined:

Grasses:

A. šáchor

E. ber

C. hedgehog corns the leg

D. oat deaf

Cyperus esculentus Setaria sp.

Echinochloa crusgalli - Avena fatua

Broadleaf weeds:

E. curly curly

F. Purple Magpie

8. abutilon

H. mustard

Rumex crispus Ipomoea purpurea Abutilon theophrasti Brassica sp.

First, broadleaf plants are sown and after 4 days grasses are sown. Numerous seeds are sown to yield 20 to 50 seedlings in a row after emergence, depending on the size of the plant.

Ten days after sowing, the grown seedlings are sprayed with all the plant species in aqueous solutions of the test active compounds. The solutions are prepared at a dilution to reach 750 liters per hectare, equivalent to 4.48 kg / ha for each active substance tested. In order to assess the effect of the active substance on each plant, tests with untreated plants are carried out simultaneously.

After 19 days, the test pans are compared to untreated and visually assessed for their effect, which is scored on a scale of 0 to 100%, with 0% indicating that the plant is the same as in the untreated control and 100% means complete destruction of all plants. in a row. are given in Table I.

Any damage to the plant is taken into account. Results'

Table I

Results of the herbicidal test

Test compound

Rate kg / ha

Percent damage

Grass

A B

Slothy weed

E F G

N-phosphonomeeylglycine, di-n-butylmethylsulphonium salt

4,48 70

100 90 90

80

2. N-phosphonomethylglycine, diethylmethylsulfonium salt

4.48 75 90

60

55 65

This example illustrates the herbicidal activity of other active compounds according to the invention.

An aluminum bowl of 15.2 x 22.9 x 8.9 cm is filled to a depth of 7.6 cm with sandy dust containing 50 ppm each of the commercial fungicide cis-N- [(trichlomethyl) thio] 4-cyclohexene-1, 2-dicarboximide (Captan) and fertilizers 17-17-17 (17% by weight nitrogen, 17% phosphorus pentoxide and 17% potassium oxide). Rows are squeezed across each bowl and the seeds of broadleaf weed plants and grasses are sown, each in a single row. The effect on the following plants shall be examined:

broadleaf weeds:

A. Purple Purple

B. beet

C. durman

D. abutilon

E. mustard

G. Pigweed

F. aubergine

Ipomoea purpurea Xanthium sp.

Aburailon theophrasti Brassica sp.

Amaaraithus sp. Solanum sp.

Grasses:

H. šáchor

I. roof brome

J. ber

K. ryegrass

L hedgehog corns leg

M. sorghum

N. oat deaf

Cyperus esculentus

Bromus spp. Setaria sp.

Lolium multiflornm EcNinoclhLoa crusgeaii Sogrum bicolor

Avéna fatua

First, broad-leaved plants are sown and after 4 days grasses are sown. Sufficient seeds are sown to yield 20 to 50 seedlings in a row after sowing, depending on the size of the plant.

Ten days after the emergence of grasses with grown seedlings of all plant species with aqueous solutions of the test active substances. The solutions are prepared at a dilution to reach 750 liters per hectare, corresponding to 0.28 to 4.48 kg / ha for each active substance tested. They are carried out to assess the effect of the active substance on each plant. also tests with untreated plants.

After 19 days, the test pans are compared to untreated and visually assessed plants with a scoring effect of 0 to 100%, with 0% indicating that the plant is the same as in the untreated control and 100% means complete destruction of all plants inline. Any damage to the plant is taken into account. The results are shown in Table II.

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Claims (6)

SUBJECT OF THE INVENTION Plant growth regulating and herbicidal composition, characterized in that it comprises an effective, natural development of plants controlling the amount or herbicidal amount of the active compound of the formula I R ³ IH ² -S ^β AND. 0 _% 0 0 P-CH ² NHCH ² COH / ^{2 2} HIM (!) 12 and wherein R ^1, R ^J, and R t each is alkyl of 1 to 6 carbon iWLíki, wherein at most two of these groups are the same, and an inert carrier · Composition according to claim 1, characterized in that it contains an active compound of the formula I, in which R ¹ , R ² and R ³ are in each case an alkyl group having 1 to 4 carbon atoms, at most two of which are the same. Composition according to claim 1, characterized in that it contains an active ingredient of the formula I, 123 wherein R 'and R denote each n-butyl group and R * ² represents a methyl group. 4. A composition according to claim 1, characterized in that it contains an active ingredient of the formula I, in which R @ 1 and R @ 2 are each a radical and R @ 1 is methyl. Composition according to claim 1, characterized in that it contains an active ingredient of the formula X, in which R ¹ and R ² are each methyl and R ³ is isopropyl. 6 · device according to claim l, characterized in that the active ingredient of the formula I wherein R ¹ and ^{R 2} k ^f res mmtylovou slíupinu and ^R3 is ^and n-butyl ·