JPH0432076B2 - - Google Patents

Description

[Detailed description of the invention]

This invention relates to new chemical compounds and their use in regulating the natural growth, or growth, of plants. In particular, the invention relates to the chemical treatment of plants to alter their natural growth and at the same time suppress undesirable plants, for the purpose of changing various agricultural or horticultural properties of the plants. It is well known to those skilled in the agricultural and horticultural arts that various beneficial effects can be obtained by altering or regulating various plant growth characteristics. For example, certain types of treatments result in a beneficial pattern of defoliation for plants. That is, further leaf growth is inhibited, while the productive plant parts are further developed. As a result, the productive parts exhibit special growth, which facilitates subsequent harvesting operations. Defoliants are particularly useful in the case of flax, cotton and bean crops, as well as other crops of a similar nature. This is not a herbicidal action because the defoliant kills the leaves but leaves other parts of the plant undamaged. In fact, it is undesirable for treated plants to wither and die when defoliating, since leaves remain attached to the withered plants. Another response exhibited by plant growth regulators is a general retardation of plant growth. This reaction has a wide variety of beneficial features. This causes the normal apical (bud) dominance to be reduced or eliminated in certain plants, resulting in the main stem becoming shorter and lateral branches increasing. This modification of natural growth results in smaller, bushier plants, which often exhibit greater resistance to drought and pest infections. Plant growth retardation is particularly preferred in the case of turfgrass. The reduced vertical growth of this type of grass increases root development resulting in a denser and stronger turf. Slowing the growth of turfgrass helps extend the time between mowing of golf courses and similar grasslands. In many plants such as silage crops, potatoes, sugar cane, sugar beets, grapes, melons and fruit trees, retarding plant growth results in increased carbohydrate content at harvest. Such growth retardation or inhibition at the appropriate growth stage of the plant reduces the effective carbohydrates consumed by plant growth, resulting in increased starch and/or sucrose content. Retarding fruit tree growth by compacting branches to create a bushy tree type often reduces vertical elongation. These considerations serve as a means of facilitating access to the fruit trees and simplifying the harvesting operation. The novel 3-mixed trialkylsulfonium salts of N-phosphonomethylglycine are used both for natural plant growth and for the control of undesirable plants.
These salts have the general formula: (In the formula, R ₁ , R ₂ and R ₃ represent C ₁ to C ₆ alkyl, and n is 0 or 1 and two or more of R ₁ , R ₂ and R ₃ are not the same.) Preferably. , R ₁ , R ₂
and R ₃ each represent C ₁ -C ₄ alkyl, R ₁ ,
Two or more of R ₂ and R ₃ are not the same. The invention also relates to a method for inhibiting the natural growth of plants. The method consists of applying an effective phytoregulatory, non-lethal dose of said compound to said plant. Furthermore, the invention relates to a method for controlling undesirable plants. The method consists of applying a herbicidally effective amount of the compound to the undesired plants during their post-emergence state. As used herein, the term "natural growth" shall refer to the normal life cycle of a plant due to its genetic characteristics and environment in the absence of external human influences. A preferred use of this compound is to increase the sucrose yield of upland sugarcane and sorghum. The word "adjustment" is used here to mean
Refers to chemical methods that do not cause plants to wither, but can bring about temporary or permanent alterations or changes in the normal life cycle. The term "herbicidally effective amount" refers to the amount of a compound disclosed herein that kills a plant or portion thereof.
"Plant" means germinating seeds, budding seedlings, and established plants, including roots and above-ground parts. Herbicidal effects include withering, defoliation, drying, shriveling,
Including leaf burn and dwarfism. Herbicidal effects are generally achieved at higher application rates than growth regulating effects. The term "alkyl" as used herein includes both straight and branched chain alkyls. Ranges of carbon atoms are intended to include their upper and lower limits. For example, methyl,
ethyl, n-propyl, isopropyl, butyl,
n-butyl, sec-butyl, pentyl, isopentyl, neopentyl, sec-pentyl, hexyl,
isohexyl, sec-hexyl, and similar groups. The term "3-mixed alkyl" refers to an alkyl substituent in a sulfonium cation that contains three alkyl moieties, but two or more of these alkyl moieties are not the same. Examples of specific compounds within the scope of the compounds represented by the above general formula are as follows. Diethylmethyl of N-phosphonoglycine Sulfonium salt Dimethylethyl of N-phosphonoglycine Sulfonium salt N-phosphonoglycine diethylisopropyl Sulfonium salt N-phosphonoglycine diethyl-n-butyl Sulfonium salt N-phosphonoglycine dimethyl -n-butylmethyl sulfonium salt N-phosphonoglycine dimethyl-n-butyl sulfonium salt N-phosphonoglycine dimethylisopropyl sulfonium salt According to the present invention, the regulation of natural growth of plants is achieved by:
This can be accomplished by applying the compound or a formulation of such compound directly to the plant or anywhere above the aerial parts about 4 to 10 weeks before harvest. With properly regulated application, growth regulation can be achieved without weeding consequences. The effective amount depends, of course, on the compound selected for treatment, as well as on the regulatory effect to be achieved, the type of plant being treated and its stage of growth, and whether a temporary or permanent effect is desired. Change. Other factors in determining the appropriate amount of phytocontrol include application method and weather conditions such as temperature or rainfall. Growth regulation occurs through the effects of compounds on either or a combination of physiological or morphological processes of the plant, or a sequence of these. Morphological changes are generally recognized by observing changes in size, shape, color or texture as well as the amount of fruit or flowers in any of the treated plants or parts thereof. On the other hand, changes in physiological processes occur within the treated plants and are usually invisible to the observer. These types of changes are often caused by the natural production, storage, or utilization of compounds, such as hormones, in plants. Following morphological changes, physiological changes become visible to the naked eye. It should be noted that numerous methods are known to those skilled in the art for determining the nature and extent of changes in various physiological processes. The compounds of this invention can be used to regulate the natural growth of treated plants in a number of ways. And it should be understood that each compound will have different regulatory effects depending on the plant type or application rate. That is, the effect varies depending on the application rate of the compound and the plant. Herbicidal effects are achieved in a similar manner and the intensity of application can be varied depending on the desired result. The compound of this invention can be prepared by reacting N-phosphonomethylglycine with silver oxide to form a silver salt, or
It can be readily prepared by reaction with sodium hydroxide to form the sodium salt and treatment of the silver or sodium salt with a trialkylsulfonium or trialkylsulfoxonium halide. Alternatively, glycine can be reacted directly with trialkylsulfonium or trialkylsulfoxonium halide in the presence of propylene oxide. N-phosphonomethylglycine is known by the common name "glyphosate" and is a commercially available raw material. this is,
It can be produced by phosphonomethylation of glycine, ie, reaction of ethylglycine with formaldehyde and diethyl phosphite, or by oxidation of N-phosphinomethylglycine. Such a method is described in U.S. Pat. No. 3,799,758 (Franz, March 26, 1974).
(Japanese) stated in the statement. As illustrated in the following examples, the compounds of this invention regulate the natural growth of plants or kill weeds. Regulatory responses are often of course desirable and their effects on crop economics always have important implications.
Thus, in assessing the significance of individual regulatory effects during plant growth, increases in yield in individual plants, increases in yield per unit area, and decreases in costs of harvest and/or subsequent operations should all be considered. should be taken into account. The following specific examples are merely illustrative and are not intended to limit the methods of making the compounds of this invention and the practice of regulating plant growth and controlling undesirable plants. Example 1 Di-n-butylmethyl sulfonium salt of N-phosphonomethylglycine In a reaction vessel, 50 ml of water, 5.1 g (0.03 mol) of N
-phosphonomethylglycine and 8.65 g (0.03 mol) of di-n-butylmethyl sulfonium iodide. Add 2.2g to this container
(0.0375 mol) of propylene oxide was charged. The entire reaction mixture was left at room temperature overnight. Finally, the reaction mixture was extracted three times with diethyl ether to separate the phases. 11.1g stripped aqueous phase
The product was obtained. This material was triturated with two 10 ml portions of tetrahydrofuran, then 10 ml of acetone, and stripped to yield 11.0 g of product. This product was further mixed with 20 ml of acetone and then with 10 ml of acetone.
ml of diethyl ether was added, triturated, and stripped. Then, 9.8 g of a low melting point solid was obtained.
The molecular structure of this product was confirmed to match that of the title compound using proton/nuclear magnetic resonance. Example 2 Diethylmethyl sulfonium salt of N-phosphonomethylglycine 50 ml water, 6.76 g (0.04 mol) N-phosphonomethylglycine, 9.3 g (0.04 mol) iodination
diethylmethyl sulfonium and 2.9g (0.05
mol) of propylene oxide were reacted overnight at room temperature as in Example 1, extracted three times with diethyl ether and then the volatiles were stripped from the aqueous phase (yield 12.3 g). Grind with acetone and diethyl ether, strip the volatiles, and weigh 12.0 g.
The title compound (decomposed at 60-65°C) was obtained. The molecular structure of the product was confirmed to match that of the title compound by proton/nuclear magnetic resonance. Example 3 Dimethylisopropyl sulfonium salt of N-phosphonomethylglycine 6.76 g (0.04 mol) N-phosphonomethylglycine, 9.3 g (0.04 mol) iodide dimethylisopropyl sulfonium and 3.5 g (0.06 mol)
of propylene oxide was reacted overnight at room temperature as in Example 1, extracted twice with diethyl ether, and the aqueous phase was stripped to determine the product (yield:
11.8g). Add this to acetone (2 10ml each)
), crush the product, and strip the product again.
11.2 g of product with n ³⁰ _D =1.5232 were obtained. The molecular structure of the product was confirmed to match that of the target compound by proton/nuclear magnetic resonance. Example 4 Dimethyl-n- of N-phosphonomethylglycine
Butyl sulfonium salt 50 ml water, 6.8 g (0.04 mol) N-phosphonomethylglycine, 10.0 g (0.04 g) iodide dimethyl-n-butyl sulfonium and 3.5 g
(0.06 mol) of propylene oxide was reacted overnight at room temperature as in Example 1, extracted twice with diethyl ether, separated the aqueous phase and stripped of volatiles to give the product (yield 12.4 g). I got it. Acetone (2 x 10 ml portions) was added, triturated and stripped to yield 12.9 g of a hygroscopic white solid. The molecular structure of each product was confirmed to match that of the title compound by proton/nuclear magnetic resonance. Other compounds within the general formula above can be prepared by any of the methods described above using appropriate starting materials. Example 5 This example illustrates the budding herbicidal activity of the compounds prepared in Examples 1 and 2. In an aluminum flat box with dimensions of 15.2 x 22.9 x 8.9 cm, commercially available fungicide cis-N [(trichloromethyl)
A sandy loam soil pot containing 50 ppm each of thio]-4-cyclohexene-1,2-dicarboximide (Captan®) and 17-17-17 fertilizer was filled to a depth of 7.6 cm. Several furrows were made across the width of each box and a variety of both grassy and broadleaf weeds were sown, one seed per furrow. The types of weeds used are as follows. Grass weeds A Yellow Nutsede Cyperus esculentus B Foxtail Setaria sp. C Watergrass Echinochloa crusgalli D Wild oat Avena fatua Broadleaf weed E Curly dock Rumex crispus F Annual morning glcry 1pomoea
purpurea G Velvetleaf Abutilon theophrasti H Mustard Brassica sp. Broad-leaved seeds were first sown and grassy seeds were sown 4 days later.
Depending on the size of each plant, ridges are applied after emergence.
Each seed was sown in sufficient quantities to produce 20 to 50 seedlings. Ten days after sowing, all types of budding seedlings were sprayed with an aqueous solution of the test compound. The solution is diluted and sprayed at a rate of 80 gallons per acre (750/ha) to achieve the preferred application rate for each test, i.e. 0.5 to 4.0 pounds of test compound per acre (0.56 to 4.48 Kg/ha). I made it so that A flat with no treatment at all was added to serve as a standard to measure the degree of weed control in the treated flat. After 19 days, each weed in each swell was visually graded using % inhibition ranging from 0% to 100% compared to the test flat standard. Here, 0% indicates the same growth rate as a standard ridge, and 100% indicates that all weeds in that ridge have completely died. All types of plant damage were taken into account. This result is the first
Shown in the table.

[Table] Butylmethyl sulfonium salt
2N-phosphonomethyl-glycine, diethyl 4.
0 75 90 90 60 60 55 65 50
methyl sulfonium salt

Methods of Application The compounds of this invention, whether used as plant regulators or herbicides, are most effective when applied to plants directly after they emerge from the soil. For agricultural field applications, the compounds are generally formulated with additional ingredients and diluent carriers to aid in spreading. Such additional ingredients and diluent carriers include water, organic solvents, powders, granules, surfactants, water-in-oil or oil-in-water suspensions, wetting agents and emulsifying agents. The formulations are generally in the form of powders, solutions, emulsifiable concentrates or wettable powders. A. Powders Powders are dense powder compositions in which the active compound is combined with a dense, free-flowing solid carrier.
When applied, it is designed to quickly settle in dry conditions and to prevent it from being carried to undesired locations by the wind. The carrier is of mineral or vegetable origin and is preferably an organic or inorganic powder of high bulk density, low surface area and low liquid absorption. Suitable carriers include micaceous talc, pyrophyllite, dense kaolin,
There is clay, tobacco waste and crushed calcium phosphate ore. The properties of powders are sometimes enhanced by the inclusion of ionic, anionic or nonionic solid or liquid wetting agents. Preferred wetting agents include alkylpenzene- or alkylnaphthalene-sulfonates, sulfated fatty alcohols, amines or acid amides, long-chain acid esters of sodium isothionate, esters of sodium fosuccinate, sulfated- or sulfonated fatty acids. These include esters, petroleum sulfonates, sulfonated vegetable oils and ditertiary acetylene glycols. Dispersants are also used in powder compositions. Typical dispersants include methyl cellulose, polyvinyl alcohol, lignin sulfonate, polymerized alkylnaphthalene sulfonate, sodium naphthalene sulfonate, polymethylene bisnaphthalene sulfonate, and sodium-N-methyl-N
(long chain acid) taurate. Additionally, powder compositions often include inert absorbent grinding aids to aid in the manufacture of the powder. Suitable grinding aids include attablekite clay, diatomaceous silica, synthetic finely divided silica, synthetic calcium and magnesium silicates. A typical powder composition usually contains 30% of the total composition.
The carrier is included at a concentration of ~90% by weight. It contains 5-50% by weight of grinding aids and up to about 1.0% by weight of wetting agents. If a dispersant is present, approx.
up to 0.5% by weight, and also includes small amounts of anticaking agents and antistatic agents. The particle size of all compositions is usually 30-50 microns. B. SOLUTIONS An aqueous solution of the active compound is prepared to deliver the required amount of active ingredient when the solution is applied at a rate of about 1 to about 200 gallons per acre. ing.
Typically, small amounts of non-phytotoxic surfactants are included, usually 0.05-0.5% by weight, to improve the wetting properties of the solution so that it is distributed over the plant surface. In this regard, anionic, cationic, nonionic, amphoteric and Zwiterionic surfactants may all be used. Suitable anionic surfactants contain 8 to 80% of the fatty chain.
There are alkali metal, ammonium, or amine salts of fatty alcohol sulfates with 18 carbon atoms and sodium salts of alkali benzenesulfonic acids with 9 to 15 carbon atoms in the alkyl chain. Suitable cationic surfactants include dimethyl dialkyl quaternary ammonium halides with alkyl chains of 8 to 18 carbon atoms. 10 for suitable nonionic surfactants.
Adduct of fatty alcohol with ~18 carbon atoms and polyoxyethylene, polyethylene oxide condensate of alkyl phenol with alkyl chain of 6-12 carbon atoms, containing 5-25% per mole of alkyl phenol. There are polyethylene oxide condensates with 10 to 40 moles of ethylene oxide bound per mole of sorbitan ester. Suitable amphoteric surfactants include one fatty acid substituent containing from 8 to 18 carbon atoms and another anionic aqueous group such as sulfate or sulfonate.
There are secondary and tertiary fatty acid amine derivatives with individual amines. Sodium-3-dodecylaminopropionate and sodium-3-dodecyl
Aminopropane sulfonate is an example. Appropriate Zbittelion surface activity includes 8
There are aliphatic quaternary ammonium compound derivatives having one aliphatic substituent containing ~18 carbon atoms and one substituent having an anionic water-soluble group. An example is 3-(N,N-dimethyl-N-hexadecyl ammonio)propane-1
-sulfonate and 3-(N,N-dimethyl-
N-heisadecyl ammonio)-2-hydroxy propane-1-sulfonate. C Emulsifying Concentrates Emulsifying concentrates are liquids in which the active ingredient and the emulsifier are dissolved in a non-aqueous solvent. Prior to use, the concentrate is diluted with water to form a suspension of solvent droplets. Typical solvents used in emulsifying concentrates include weed oils, chlorinated hydrocarbons, and water-immiscible ethers and ketones. Typical emulsifiers include anionic or nonionic surfactants or mixtures of the two. Examples include long-chain marker butane polyethoxy alcohols, alkylaryl polyethoxy alcohols, sorbitan fatty acid esters, polyoxyethylene ethers of sorbitan fatty acid esters, polyoxyethylene glycol esters of fatty- or rosin-acids, fatty alcohol amide condensates, There are calcium or amine salts of fatty alcohol sulfates, oil-soluble petroleum sulfonates or mixtures of these emulsifiers. These emulsifiers usually comprise about 1 to 10% by weight of the total composition. A typical emulsifying concentrate is approximately 15 to 50% by weight,
It contains active ingredients, about 40-82% by weight solvent, and about 1-10% by weight emulsifier. Other additives such as spreading agents and adhesives are also included. D. Lubricating Powders Lubricating powders are water-dispersible compositions containing active ingredients, inert solids, diluents, and one or more surfactants that wet quickly when dispersed in water. , to prevent clumping. Suitable spreading agents include natural minerals and materials synthesized from such minerals. For example, kaolinite, atable guide clay, montmorillonite viscosity, synthetic silica, synthetic magnesium,
Silicates and calcium sulfate dihydrate. Suitable surfactants, both nonionic and anionic, act as wetting agents and dispersing agents. Usually one of each type is included. Preferred wetting agents include alkylbenzenes or alkylnaphthalene sulfonates, sulfated fatty alcohols, amines or acid amides, long chain acid esters of sodium isothionate, esters of sodium sulfocinate, sulfated or sulfonated fatty acid esters, petroleum sulfonates and sulfonated vegetable oils. and Jitashaari
Contains acetylene glycol. Preferred dispersants are methylcellulose, polyvinyl alcohol lignin sulfonate, polymerized alkylnaphthalene sulfonate, sodium naphthalene sulfonate, polymethylene bisnaphthalene sulfonate and sodium-N-methyl-N-(long chain acid) taurate. A typical wettable powder contains 25-90% active ingredient, 0.5-2.0% wetting agent, 0.25-5.0% dispersant, and 9.25-74.25% inert diluent. often,
0.1-1.0% of the diluent is replaced with corrosion inhibitors and/or antifoaming agents. E. General In general, any post-emergence application method can be used, but
Customary sparging or spraying equipment is used for this purpose. The amount of active ingredient effective to produce the desired result of herbicidal or growth control depends on the type of plant to be controlled and the application conditions. Herbicidal efficacy is usually achieved at 0.5 to 50 pounds of active ingredient per acre, preferably 1 to 10 pounds, while plant growth control is usually achieved at 0.1 to 20 pounds of active ingredient per acre.
lbs., preferably 0.5 to 5 lbs. It is very clear to those skilled in the art that less active compounds need to be used in higher amounts than higher active compounds in order to achieve the same degree of inhibition. .

Claims (1)

[Claims] 1. General formula (wherein R ₁ , R ₂ and R ₃ represent C ₁ -C ₆ alkyl, and n is 0 or 1, R ₁ , R ₂ and R ₃
three of which are not the same). 2. The compound according to claim 1, wherein n is 0. 3. A compound according to claim 2, wherein _R1 , _R2 and _R3 each represent _C1 - _C4 alkyl. 4. A compound according to claim 2, wherein R ₁ and R ₂ are each n-butyl and R ₃ is methyl. 5 R ₁ and R ₂ are each ethyl, and
3. A compound according to claim 2, wherein R ₃ is methyl. 6 R ₁ and R ₂ are each methyl, and
3. A compound according to claim 2, wherein R ₃ is isopropyl. 7 R ₁ and R ₂ are each methyl, and
_3. A compound according to claim 2, wherein R3 is n-butyl. 8 General formula (wherein R ₁ , R ₂ and R ₃ represent C ₁ -C ₆ alkyl, and n is 0 or 1, R ₁ , R ₂ and R ₃
A herbicidal composition comprising an inert diluent carrier and a herbicidally effective amount of a compound having the following three of which are not the same. 9. The herbicidal composition according to claim 8, wherein n is 0. 10. The herbicidal composition according to claim 8, wherein _R1 , _R2 and _R3 are each _C1 - _C4 alkyl. 11 R ₁ and R ₂ are each n-butyl,
The herbicidal composition according to claim 8, wherein R ₃ is methyl. 12. The herbicidal composition according to claim 9, wherein R ₁ and R ₂ are each ethyl and R ₃ is methyl. 13 Claim 9, wherein R ₁ and R ₂ are each methyl and R ₃ is isopropyl
The herbicidal composition described in . 14. The herbicidal composition according to claim 9, wherein R ₁ and R ₂ are each methyl, and R ₃ is n-butyl. 15 General formula (wherein R ₁ , R ₂ and R ₃ represent C ₁ -C ₆ alkyl, and n is 0 or 1, R ₁ , R ₂ and R ₃
A method for suppressing undesirable plants, which comprises applying a herbicidal composition comprising a herbicidally effective amount of a compound having the following three of which are different from each other and an inert diluent carrier to a plant in a post-emergence state. 16. The method for suppressing undesirable plants according to claim 15, wherein n is 0. 17. A method for controlling undesirable plants according to claim 16, wherein _R1 , _R2 and _R3 each represent _C1 - _C4 alkyl. 18 R ₁ and R ₂ are each n-butyl,
and claim 16, wherein R ₃ is methyl.
A method for suppressing undesirable plants as described in Section 1. 19. The method of controlling undesirable plants according to claim 16, wherein R ₁ and R ₂ are each ethyl and R ₃ is methyl. 20 Claim 1 in which R ₁ and R ₂ are each methyl and R ₃ is isopropyl
7. A method for suppressing undesirable plants according to item 6. 21 Claim 16, wherein R ₁ and R ₂ are each methyl and R ₃ is n-butyl
A method for suppressing undesirable plants as described in Section 1.