KR870000659B1 - Preparation of trialkylsulfonium salts of n-phosphonomethyl glycine - Google Patents

Abstract

[R1S+(O)nR2R3 [O-P(O)(OH)CH2NHCH2CO2H (R1,R2,R3=C1-6alkyl; n=0,1) are prepd. Thus, (HO)2P(O)CH2NHCH2CO2H is treated with Et2S+MeI- to give [Ot2S+Me [O-P(O)(OH)CH2NHCH2CO2H (I). (I) are useful as plant growth regulators (applicn. rate 0.1-20(pref. 0.5-5)1b/acre) and post-emergence herbicides(applicn. rate 0.1-50 (pref. 1-10)1b/ acre).

Description

[Name of invention]

Method for producing trialkylsulfonium salts of N-phosphono methylglycine.

Detailed description of the invention

The present invention relates to a process for the preparation of tri-mixed alkylsulfonium salts of N-phosphono methylglycines having the following general formula useful for controlling the natural growth of plants and for suppressing unnecessary plants.

Wherein R ₁ , R ₂ , and R ₃ are C ₂ -C ₆ alkyl, wherein two or more of R ₁ , R ₂ , and R ₃ are not identical. Preferably R ₁ , R ₂ , and R ₃ are C ₁ -C ₄ alkyl, wherein two or more of R ₁ , R ₂ , and R ₃ are not the same.

In addition, the present invention provides a method for regulating the natural growth of a plant obtained by applying a plant control, an effective and non-fatty amount of the compound to the plant, and an effective amount of the compound in the plant at the post-germination stage. It relates to a method for suppressing unnecessary plants made by applying to the.

As used herein, "natural growth or development" refers to the normal life cycle of a plant according to the heredity and environment of the plant without artificial external influences. Shoes of the Invention "

By "herbicidally effective amount" is meant the amount of a compound specified herein that can kill a plant or part thereof. "Plant" means a settled plant including germinating seeds, growing seedlings, roots and ground parts. Herbicidal effects include killing, deciduous leaves, drying, atrophy, dead leaves and dwarfization, etc. In general, the herbicidal effect is higher than the growth control effect.

As used herein, "alkyl" includes both straight and branched chain alkyl groups. The carbon atom range includes both upper and lower limits thereof, for example methyl, ethyl, n-propyl, isopropyl, butyl, n-butyl, second -butyl, pentyl, isopentyl, neopentyl, second- Pentyl. Hexyl, second-hexyl and the like. Thus, the term "trimixed alkyl" denotes an alkyl substitution where the sulfonium cation contains three alkyllots. However, two or more of the alkyllots are not identical.

Examples of the compound corresponding to the general formula are as follows.

Diethylmethylsulfonium Salt of N-phosphonoglycine

Dimethylethyl sulfonium salt of N-phosphonoglycine

Diethylisopropyl Sulfonium Salt of N-phosphonoglycine

Diethyl-n-butyl sulfonium salt of N-phosphonoglyco

Di-n-butylmethyl sulfonium salt of N-phosphonoglycine

Dimethyl-n-butyl sulfonium salt of N-phosphonoglycine

Dimethylisopropyl sulfonium salt of N-phosphonoglycine

According to the present invention, the control of the natural growth or development of the plant is achieved by applying the compound of the general formula or the composition thereof directly to the plant about 4-10 weeks before harvesting. By appropriately controlled action, the growth regulation effect of the plant can be achieved by a method other than the herbicidal effect. The effective amount depends not only on the particular substance selected, but also on the required regulatory effect, the type of plant to be treated, its developmental relationship and whether it is intended for a permanent or temporary treatment effect. Other factors to be considered in determining the appropriate amount of plant control include the method of application and climatic conditions such as temperature or rainfall. Growth regulation effects occur in the ecological process or form of the plant, or both, or by the effect of the compound. Ecological changes are manifested not only by changes in the amount of fruit or flower produced, but also by observable changes in the size, shape, color or texture of the plant.

On the other hand, changes in ecological processes occur in the treated plants and are usually invisible to the observer's eyes. These ecological changes frequently occur in the production, storage or use of chemicals such as hormones that occur naturally in plants. Ecological changes can be detected with the naked eye when a change of form follows. In addition, numerous analytical procedures for measuring the nature and magnitude of changes in various ecological processes are well known to those skilled in the art.

The compounds of the present invention are useful for controlling the natural growth or development of treated plants in various ways. And it should be understood that individual compounds may not exhibit the same regulatory effects in individual plant species or at individual rates of application. As mentioned above, the modulating effect will vary depending on the compound, application rate, plant and the like.

The herbicidal effect is also achieved in the same way, and the intensity of the application rate may be varied to achieve the desired result.

The compounds of the present invention can be easily prepared by the following process.

That is, the compound of the present invention forms a silver salt by reacting N-phosphono methylglycine with silver oxide or forms a sodium salt by reacting N-phosphono methylglycine with sodium hydroxide, By treating the silver or sodium salt with trialkylsulfonium or trialkylsulfonium halide. Alternatively, glycine may be reacted directly with trialkylsulfonium or halogenated trialkyl sulfoxium in the presence of propylene oxide. N-phosphonomethylglycine is a commercially available substance known as the "glyphosate". It can be prepared by phosphonomethylation of glycine, reaction of ethylglycine acid with formaldehyde and diethylphosphite, or oxidation of N-phosphonomethylglycine. Such manufacturing methods are described in US Pat. No. 3,799,758 (Franz, March 26, 1974).

As described in the Examples below, the compounds of the present invention can control the natural growth or development of plants or kill weeds. The modulatory effect is desirable as the compound's inherent properties, while the effect of these compounds is of paramount importance in the agricultural production economy.

The following specific examples are examples of methods for preparing compounds according to the invention and the effectiveness of these compounds in controlling plant growth and suppressing unwanted plants, the invention being not limited to the following examples.

Example I

Di-n-butylmethyl sulfonium salt of N-phosphonomethylglycine

The reaction vessel was charged with 50 ml of water, 5.1 g (0.03 mol) N-phosphono methylglycine and 8.65 (0.03 mol) iodide di-n-butylmethyl sulfosonyl.

The reaction vessel was further charged with 2.2 g (0.0375 mol) of propylene oxide. The whole reaction mixture was left at room temperature overnight. At the end of this time, the reaction mixture was extracted three times with diethyl ether and phase separated. Stripping the aqueous phase yielded 11.1 g of product. This product was triturated with tetrahydrofuran (2 x 10 ml), then triturated and stripped with 10 ml of acetone to yield 11.0 g of product. The product was further ground with 20 ml of acetone, and then ground and stripped with 10 ml of diethyl ether to yield 9.8 g of low-condensed solid product. The molecular structure of the product was identified as the title compound by proton-nuclear magnetic resonance analysis.

Example II

Diethylmethylsulfonium Salt of N-phosphono methylglycine

In a procedure similar to Example I, 50 ml of water, 6.76 g (0.04 mole) of N-phosphonomethlglycine, 9.3 g (0.04 mole) of diethyl methylsulfonsonyl iodide and 2.9 g (0.05 mole) After propylene oxide was reacted overnight at room temperature, the mixture was extracted three times with diethyl ether, and 12.3 g of product was produced by stripping the volatile phase of the aqueous phase. After trituration with acetone and diethyl ether, 12.0 g of the title compound (decomposition at 60-65 ° C.) was obtained by stripping the volatiles. The molecular structure of the product was identified as the molecular structure of the title compound by proton-nuclear magnetic resonance analysis.

Example III

Dimethylisopropyl sulfonium salt of N-phosphonomethylglycine

In a procedure similar to Example I, 50 ml of water, 6.76 g (0.04 mole) N-phosphonomethylglycine, 9.3 g (0.04 mole) iodide dimethylisopropyl sulfosonyl and 3.5 g (0.06 mole) propylene oxide Was reacted overnight at room temperature, then extracted twice with diethyl ether, and stripping the aqueous phase yielded 11.8 g of product. 11.2 g product (nD ³⁰ 1.5232) was obtained by stripping the product again with acetone (twice, 10 ml each) and after grinding. The molecular structure of this product was confirmed as the molecular structure of the title compound by proton-nuclear magnetic resonance analysis.

Example IV

Dimethyl-n-butyl sulfonium salt of N-phosphonomethylglycine

In a procedure similar to Example I, 50 ml of water, 6.8 g (0.04 mol) N-phosphonomethylglycine, 10.0 g (0.04 mol) dimethyl-n-butyl sulfoxonyl iodide and 3.5 g (0.06 mol) After overnight reaction of propylene oxide at room temperature, the mixture was extracted twice with diethyl ether, phase separated, and the volatiles were stripped to yield 12.4 g of product. 12.9 g of hygroscopic white solid was obtained by grinding with acetone (2 times, 10 ml each) and stripping. The molecular structure of this product was identified as the title compound by proton-nuclear magnetic resonance analysis.

Other compounds within the scope of the above general formula can be prepared by any of the above methods as suitable starting materials.

Example V

This example describes the herbicidal activity after germination of the compounds prepared in Examples I and II.

50 ppm each of the commercially available disinfectant cis-N [(trichloromethyl) rio] -4-cyclohexene-1, 2-dicarboximide (Captan ^R ) and 17- in aluminum growers (15.2 × 22.9 × 8.9 cm) Filled loam soil containing 17-17 fertilizer (wt% of NP ₂ P ₅ -K ₂ O) was filled to a depth of 7.6 cm. After making several bones in the width direction of each grower, seeds of various grasses and broadleaf weeds were sown one seed per bone. Weed species used are as follows.

Poole:

A. Yellow Nut Sage Cyperus esculentus

B. Weaver Setaria sp.

C. Watergrass Echinochloa crusgalli

D. Oat grass Avena fatua

Broadleaf weeds:

E. Curry Dog Rumex crispus

F. Annual Morning Glory Ipomoea purpurea

G. Velvet Leaf Abutilon theophrasti

H. Mustard Brassica sp.

Four days after the seedlings were sown, the grass types were sown. A sufficient amount of seeds of each kind was sown so that after germination depending on the size of each plant, 20-50 seedlings per bone were allowed.

After 10 days of sowing, all germinated seedlings were sprayed with an aqueous solution of the test compound. The solution was diluted to a spray rate of 80 gallons per acre (750 liters per hectare) of 4.0 pounds of test compound per acre (4.48 kg per hectare). Additional growers that were not treated at all were used as a criterion to measure and compare the degree of weed inhibition in the treated growers.

After 19 days, the test cultivators were compared with the standard, and the weeds of each bone were evaluated visually by converting the weeds into 0% to 100% of inhibition%. Where 0% represents the same growth rate as the reference bone, and 100% indicates complete killing of all weeds in the bone. Injuries of all types of plants were evaluated. The results are shown in Table I.

TABLE I

Weeding test result

Application method

Whether used as a plant growth regulator or as a herbicide, the compounds of the present invention are most useful when the plant germinates from soil and subsequently applied directly to the plant. For use in cropland, the compounds are generally made into suitable compositions containing additional ingredients and diluent carriers to aid their dispersion. Such components or carriers are, for example, water, organic solvents, powders, granules, surfactants, water in oils and oil emulsions in water, wetting agents, dispersing agents and emulsifiers. Usually the composition takes the form of a powder, solution, emulsion concentrate or wet powder.

A. Powder

The powder is a dense powder composition in which the active compound and the free, dense solid carrier are combined. These are intended to be adapted to dry form and are intended to prevent wind blown and settling in unwanted areas.

The carrier may be a mineral or plant-based material, but an organic or inorganic powder having a high density, small surface area and low liquid absorption is preferable as the carrier. Suitable carriers include mica talc, lobite, kaolin, tobacco dust and ground calcium phosphorus.

The performance of the powder is improved by incorporating liquid or solid humectants with ionic, anionic or nonionic properties from time to time. Preferred humectants include alkylbenzenes, alkylnaphthalene sulfonates, sulfided fats, ie alcohols, amines or acid amides, acid esters of long-chain sodium isotionates, esters of sodium sulfosuccinates, sulfides or sulfates These include phonated aliphatic acid esters, petroleum sulfonates, sulfonated vegetable oils and dietary acetylene glycols. Dispersing medium in the powder composition is also useful. Typical solvents include methyl cellulose, polyvinyl alcohol, lignin sulfonate, synthetic alkylnaphthalene sulfonate, sodium naphthalene sulfonate, polymethylene bisnaphthylene sulfonate and sodium-N-methyl-N- (long chain acid) taurate. This includes this.

In addition, in the preparation of the powder, an inert adsorbent chain adjuvant is often included in the powder composition. Suitable grinding aids include attapulgite clay, diatomaceous earth, synthetic purified diatomaceous earth, synthetic calcium silicates and magnesium, and the like.

In typical powder compositions, the carrier is usually present at a concentration of about 30-90% by weight of the total composition. Grinding aids are usually present in amounts of about 5-50% by weight, and wetting agents within about 1.0% by weight. When a dispersion medium is used, it is present in an amount within about 0.5% by weight, and small amounts of anti-caking agents and antistatic agents may also be present. The particle size of the total composition is usually about 30-50 microns.

B. Solution

The aqueous solution of the active compound has an application rate of about 1 to 200 gallons per acre (about per hectare)

Suitable anionic surfactants include amine salts of aliphatic alcohol sulfates having 8 to 18 carbon atoms in alkali metals, ammonium and aliphatic chains, and sodium salts of alkyl benzenesulfonates having 9 to 15 carbon atoms in the alkyl chains. Include. Suitable cationic surfactants include dimethyl dialkyl halide ammonium having an alkyl chain of 8 to 18 carbon atoms. Suitable nonionic surfactants include polyoxyethylene adducts of aliphatic alcohols with 10-18 carbon atoms, alkyl chains of 6-12 carbon atoms and alkylphenols with 5-25 ethylene oxide condensed on each mole of alkylphenol. Polyethylene oxide condensate, and oxidized polyethylene condensate of sorbitan esters having 10-40 moles of ethylene oxide condensate condensed on each mole sorbitan ester. Suitable amphoteric surfactants include second and third aliphatic amine derivatives containing aliphatic substituents containing 8-18 carbon atoms and containing anionic water-soluble groups such as sulfate or sulfonate. Examples include sodium-3-dodecylaminopropionate and sodium-3-dodecyl aminopropane sulfonate. Suitable amphoteric surfactants include derivatives of aliphatic quaternary ammonium compounds having aliphatic substitutions containing 8-18 carbon atoms and another aliphatic substitution containing anionic water-soluble groups. For example, 3- (N, N-dimethyl-N-hexadecyl ammonia) propane-1-sulfonate and 3- (N, N-dimethyl-N-hexadecyl ammonia) -2-hydroxypropane-1- Sulfone

C. Emulsified Concentrates

Emulsified concentrates are solutions in which the active substance and emulsifier are dissolved in a non-water-miscible solvent. Prior to use, the concentrate is diluted with water to form a solvent emulsion suspension emulsion.

Typical solvents used in emulsified concentrates include weed oil, hydrocarbon chlorides, non-miscible ethers, esters and ketones.

Typical emulsifiers are anionic or nonionic surfactants or mixtures thereof. For example, long-chain mercaptanpolyethoxyalcohols, alkylarylpolyethoxyalcohols, sorbitan fatty acid esters, polyoxyethylene ethers with sorbitan fatty acid esters, polyoxyethylene glycle esters with fatty acids or rosin acids, aliphatic Alkylol amide concentrates, calcium and amine salts of aliphatic alcohol sulfates, oil-soluble petroleum sulfonates, preferably mixtures of these emulsifiers, and the like. Usually such emulsifiers comprise about 1-10% by weight of the total composition.

Typical emulsion concentrates contain about 15-50% by weight of active material, about 40-82% by weight of solvent and about 1-10% by weight of emulsifier. Other additives such as prosthetics and stickers may also be included.

D. Wet Powder

Wet powders are water dispersible compositions containing the active material, an inert solid weight agent and one or more surfactants to provide rapid wetting and anti-coagulation properties when suspended in water.

Suitable solid weight agents may be derived from natural minerals and materials derived from such minerals.

Suitable surfactants include both nonionic and anionic types, and act as humectants and dispersion media, usually including one of them. Preferred wetting agents are alkylbenzenes and alkylnaphthalene sulfonates, sulfonated aliphatic alcohols, amines or acid amides, long chain esters of sodium isotionate, esters of natrium sulfosuccisate, cyclized or sulfonated fatty acid esters, petrosulfonates, These include sulfonated vegetable oils and dietary acetylene glycols. Preferred dispersion media are methyl cellulose, polyvinyl alcohol, lignin sulfonate, polymerized alkylnaphthalene sulfonate, sodium naphthalene sulfonate, polymethylene bisnaphthalene sulfonate and sodium-N-methyl-N- (long chain acid) taurate and the like.

劑) 및 또는 기포방지제로 대치된다.Typical wetting powders contain 25-90% active material, 0.5-2.0% wetting agent, 0.25-5.0% dispersion medium and 925-74.25% by weight inert weighting agent. Sometimes 0.1 to 1.0% by weight of the rust inhibitor

V) and / or antifoaming agents.

E. Generality

In general, any conventional application may be used, including post-germination spraying and spraying. Whether used as a herbicide or as a growth regulator, the amount of active ingredient effective to achieve the desired result depends on the nature and main conditions of the plant species to be controlled. The herbicidal effect usually consists of 0.1 to 50 pounds per acre, preferably 1 to 10 pounds of active ingredient, while the plant growth control effect is usually achieved with an active ingredient of pounds per acre, preferably 0.1 to 20 pounds. Low activity unity to achieve the same degree of inhibition

Claims (7)

3-mixed alkyl of N-phosphono methylglycine with the following general formula consisting of reacting N-phosphonomethylglycine with sodium hydroxide to form sodium salt, followed by treatment with trialkylsulfonium or halogenated trialkylsulfonium Method for preparing sulfonium salts.

Expression, R ₁ , R ₂ and R ₃ are C ₁ -C ₅ alkyl, n is 0 or 1 and not all three of R ₁ , R ₂ or R ₃ are identical. The method according to claim 1, wherein n is 0. 3. The process according to claim 2, wherein R ₁ , R ₂ and R ₃ each represent C ₁ -C ₄ alkyl. 3. The process according to claim 2, wherein R ₁ and R ₂ are each n-butyl and R ₃ is methyl. 3. The process according to claim 2, wherein R ₁ and R ₂ are each ethyl and R ₃ is methyl. The process according to claim 2, wherein R ₁ and R ₂ are each methyl and R ₃ is isopropyl. 3. The process according to claim 2, wherein R ₁ and R ₂ are each methyl and R ₃ is n-butyl.