JPS59101500A - Aluminum n-phosphonomethylglycine and use as herbicide - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION This application is filed under No. 4442., filed on November 16, 1982.
This is a partial continuation of the No. 027 application.

The present invention relates to novel compounds and their use as weed suppressants and for regulating the natural growth of plants.

various stages of plant growth are altered or improved;
It is well known that many favorable results have been obtained. For example, the waste parts of plants may be left ungrown so that the parts useful as crops are not affected. In this way, the parts useful as crops can be specially grown, and the harvesting work can be made more efficient.

Chemical agents containing such effects are particularly useful for flax, cotton, beans, and other crops of this nature. Although defoliation helps the leaves, it does not damage other parts of the plant, so it is not a herbicide. In fact, if you are looking for fallen leaves,
If the treated plants are killed, the leaves will remain attached to the dead plants, which is undesirable.

Another effect of plant growth regulators is to generally retard plant growth. This action has a wide range of benefits. In some plants, the growth momentum toward the apex decreases, the length of the main stem becomes shorter, and the number of branches to the stem increases. It grows short and thick, and has good resistance to early growth and insect damage.

The plant growth retardant also suppresses the vertical growth of turfgrass, improves root filtration, and makes it denser and better! If it helps create a lush lawn5, grass growth control can also help lengthen the time between mowing on golf courses and other grassy areas.

Hensley et al., Weed Research, 1978, Vol. 18, pp. 287-291, describes the role of various cations in the action of N-phosphonomethylglycine. The presence of aluminum in clay or organic matter causes N
- It was found that the root growth inhibitory effect of phosphonomethylglycine was rendered inactive or significantly reduced.

The inactivation of the toxic effect by the presence of aluminum has therefore been demonstrated in this literature. A biological evaluation was conducted to determine the extent of N-phosphonomethylglycine uptake by various cations in sorghum hybrids. It has been hypothesized that aluminum is sichelated by N-phosphonomethylglycine, which inactivates it. The invention according to the present invention is the opposite.

Hanson et al., at the 26th U.S. Weed Science Society 2, show that N-phosphonomethylglycine forms aluminum complexes that adsorb onto mineral colloids and organic compounds.

Sprunkej/l/ (5prankej) and others, Weed Science x (Weed 5science) 23
Vol. 229-234 shows that N-phosphonomethylglycine is rapidly inactivated in organic and mineral soils, and that aluminum-containing saturated clays and organic materials are more susceptible to unsaturated and non-aluminum-containing materials. It also shows that more N-phosphonomethylglycine was absorbed. Sprankel et al. hypothesize that N-phosphonomethylglycine is bound to aluminum-containing soils and rendered inactive. Furthermore, the following literature also reports a decrease in the phytotoxicity of N-phosphonomethylglycine due to the presence of aluminum. ; Wills, e. (Wills) 1973
Ab8tr.

weeci, scr, soc, m, ,
Page 59: philips x 1
975, prQC, North Cent.

Weed (:'ontroJ Conf, 30.
115 pages.

Aluminum N-phosphonomethylglycine, when used in herbicidally effective amounts, has been found to be a novel compound that has agricultural utility, such as total control over the natural growth of plants. Therefore, the present invention relates to a method for suppressing unnecessary plant growth by applying the herbicidal efficacy of the present compound to plants after germination. Herbicidal effects are usually achieved at high application rates as well as plant growth regulating effects. This compound is particularly effective in controlling weeds. "Herbicidal effective amount" refers to the amount that kills plants or parts thereof. "Plants" include germinating seeds, germinated plants, and sweat plants, including their roots and above-ground parts. Additionally, aluminum N-phosphonomethylglycine has been found to contain significant desirable properties not shown in the prior art.

The herbicidal effect can be achieved by inhibiting the natural growth of the plant, and the degree of herbicide application depends on the degree of weeding desired. The compounds of the invention can be treated in a variety of ways.
helps regulate the natural growth of plants. The regulatory effect varies depending on the type of plant and the rate of application of the herbicide. The compounds of the invention are easily obtained by reacting N-phosphonomethylglycine with an aluminum source in the presence of water to form an aqueous solution.

When taking this method for preparing the compounds of the present invention, N
- The molar ratio of aluminum cation to phosphonomethylglycine was found to be 1 to 4. In addition, the present compound also reacts aluminum salts such as aluminum inonolophoxide with an aqueous solution of N-phosphonomethylglycine. You can get it even if you let it. After heating under reflux for the required time, the product is cooled, filtered,
Obtained by concentrating p liquid. Naturally, the aluminum source is selected from a wide range of organic or inorganic aluminum compounds.

The aluminum source may be in the form of commercially available aluminum oxide, aluminum hydroxide.

N-phosphonomethylglycine is a commercially available compound obtained by oxidation of D,N-phosphinomethylglycine by reaction with phosphonomethylation of glycine or ethylchlycine-)t-formaldehyde and diethyl phosphite.

These methods are described in U.S. Pat. No. 3,799,758 (7
Lantz, March 26, 1974).

Examples 1 and 2 IIi illustrate the preparation of aluminum compounds, and Examples 3 and 4 demonstrate non-selective herbicidal and plant growth activities. It is merely illustrative, not limiting, of the regulatory effects on plants.

Example 1 Aluminum N-phosphonomethylglycine (1,17F) in a flask containing 20 (Lm) of deionized water.

0.015 mol) k 7.5 f (0.045 mol) mixed with N-yhsphonomethylglycine. The flask is equipped with a magnetic stirrer. The solution was heated at total reflux temperature for 1 hour and then left at room temperature overnight. The next day, -
After cooling overnight, the reaction mixture contained much more solids. This was heated to reflux for an additional 3 hours and then cooled to room temperature. This was filtered to remove solids and stored in Fr& at 30° C. and 1 wm of mercury.

The residue was a white powder of f-18, Of, which was water-soluble and part Q11 was plated at 231°C. This white powder was subjected to standard analytical procedures and was found to consist of 1 part aluminum and 4 parts N-phosphonomethylglycine anion.

Example 2 Aluminum hydroxide (1,02F.

0.005 mol) and N-phosphonomethylglycine (0,
02 moles, 3.338f ) if 5 oy of water 111! dropwise and briefly heated to reflux temperature to dissolve the reactants. This compound is soluble in water. The analysis results are as follows.

Theoretical value - carbon 18.65%, hydrogen 4.79%, reference 7
．． 25%, phosphorus 16.06%, aluminum 3.49
%, actual values - carbon 18.79%, hydrogen 4.59%, hydrogen 7.39%, phosphorus 16.34%, aluminum 3
．． 50%, this analysis corresponds to 1 part of aluminum tetrahydrate per 4 Ifll of N-phosphonometherglycine.

Transmission electron microscopy (t
transmission electron m1cr
osc.

-py)2 was used to determine nine turns of small crystal elmcroton diffraction for the compounds of the invention.

Different triclinic unit cells (tric-1i
Three phases were measured using a nic unit cell) f. Below is the unit cell i4 meter (un
it cell parameters) f.

1 2 3 11-■-11-----1. --■-m---1A
27.53A 22.91A 20.32
AB 19.5OA 16.22A 1
4.39AC18,61A 18.46A 1
All lines of the 8.51AX ray diffraction pattern 56 are accounted for by these 3-unit cells. The range of reflection for aluminum compounds is 2.57-14.2A, -
The range of 10,000 N-phosphonomethylglycine is 1.37 to 8.
NMR of 37A, 7, in aqueous solution shows that a very complex dynamic equilibrium exists around it. In a solid state, an aluminum compound exists in the above structure for 1'J, so it is difficult to show one specific structure for an aluminum compound.

Example 3 Herbicidal Activity This example shows a series of post-emergence herbicidal activities of compounds of the invention.

A commercially available fungicide, cis-N[(trichloromethylnotio]-4-cyclohexene-1,2-nocal), was added to an aluminum planter measuring 15.2 x 22.9 -17-17
Fertilizer (N-p2o, -20% by weight)? 5 each
loamy 5an containing 0 ppm
d 5 oil ) f filled to a depth of 7.6 cm.

Plant rows in each noranter with various grasses and broadleaf plants? I planted it. These types are shown below.

grass DB downybrom
e) ARG annual ryegrass (annua
l ryegrass ) punishment water glass
(watergrass) SHC Canada:
y (5battercane) WO wild oats (wild oats) F, T 7 foxtail (foxtail) broadleaf weed SES
ia ) VL Helhe 7 Tory 7 (v
eJvetleaf) German mustard (
5 tard) SP sickle yfe tsup
(sicklepod)pw hitr+:z-
pigweed crops soy soybeans RE
Rice (Ce) COT Cotton
(cotton)CN) corn (c
orn) ■ wheat (wheat) ML mi0 (milo)8B
Sugar beetsOther YNG Yellow Natsuetsuji (yeJIown
utsedge) Broad-leafed whole grasses were sown first and grasses were sown 4 days later. Depending on the size of each plant, enough seeds were sown to produce 4-5(1) i in each row after germination.

All kinds of iK water-soluble ff of the test compound of the present invention that germinated in 10 days after sowing grass! *Sprayed. As shown in each sample, this solution was rated at 80 gallons per
Nieker (750t/ha) is 0.25-2.0
Pound of compound/kneaker (0,28-2.24 kg
/hectare). Planters without any treatment were also used as a standard for comparison of degree of weed control.

After 19 days, the test planter was compared with the standard, and the weeds in each row were visually observed to determine the suppression effect of 0 to 100% (7%). 0% means the same growth as the standard;
100% completely kills weeds. All types of plant damage were also taken into account. The results are shown in Table I.

Table ■ Herbicidal test results Test compound Nialuminum N-phosphonomethylglycine 1/4 50100 30 70 70 30
58 01/2 60100 40 90 8
0 6573451 70100 55100
100 8084702 80100 80
100 100 959375 Application rate Broad leaf (lb/A) AMG CB SES VL MD
SP PW 'l'-! 1/4 60 40 40
50 75 5040 511/2 65 50
70 70 80 6050 641 70 70
75 75 90 6560 722 75 8
5 80 80100 7070 801/4 45
0 50 70 60 40 451/2 55
40 60 90 75 75 701 60 50
70 100100 90 752 75 95
80 100100100 85 Example 4 In this example, the compound of the present invention was applied to sorghum (B
sweet SorghIIn(Sorghum Vul.
gare ) ) in growth regulation.

The following test method was used.

In a series of 5X5X5 inch fiber pots, 17-17-
A loam sandy top containing 1501) l)m of 17 fertilizer was filled. A row of seeds were sown in each pot of sugar bean gold and placed in a greenhouse maintained at 27°C during the day and 21°C at night.

During the following 5 weeks, germinated plants were thinned down to 2 per pot. Po:,/)K
u Feed 17-17-17 fertilizer regularly.

Approximately 8 weeks after sowing, add acetone and water, etc. (1:
1) A solution of a test compound dissolved in a mixture containing 0.5% Tween 20 (polyoxyethylene sorbitan monolaurate) was sprayed onto plants. One method of spraying is a linear spray table. The test solution is 80 gallons/keeper (75 Ut/ha). The concentration of the solution is predetermined to give the desired application rate (lbs/keeker) when a total volume of 80 gallons/keeker is applied to the plants. The concentration is chosen to correspond to an application rate of 0.0625, 0.125, 0.25 lb/neeker (0.074, 0.15, 0.287 to 97 ha).

The plants were kept in the greenhouse for an additional 14 days.

Sugar content was measured 5 days after cutting the entire stem at the soil surface. Squeeze the stem to remove a few drops of pith sap. Total dissolved solids % (T, DS%) of this liquid? It is measured with a manual refractometer and is expressed as a percentage of the weight of the juice.

Each application rate was repeated twice, and untreated plants were also tested for comparison. The results are shown in Table H and Table ■.

Table ■ shows the symptoms and % of total dissolved solids.

The data displayed is the average value of each replicate. Table ■ shows the average total dissolved solids at each application rate. Looking at this, it can be seen that the total dissolved solid content has increased compared to the comparative example.

Table H 23St, Ch 7.1 2 0 4.5 1 0 0 Clan St: Internodal shortening Ch: Chlorosis The underline indicates the main symptoms.

Table ■ 1/4 6.5 33 1/8 5.7 16 1/16 4.5 -8 0 4.9
Methods of Application Whether used as plant growth regulators or herbicides, the compounds of this invention are most useful when applied directly to plants as they emerge from the soil. When applied in fields, additives or carriers are usually mixed in to improve dispersion. Examples of such additives and carriers are water, organic solvents, powders, granules, surfactants, water-in-oil or oil-in-water emulsions, wetting agents, dispersants, emulsifiers.

Compounds include suitable ingredients, powder, solution, emulsifiable concentrate, and melif.
``i.takes the form of a wettable powder.

A. Powder Powder is a dense powder composition in which the active ingredient is bound to a free-flowing solid carrier of heavy specific gravity. They are intended for use in dry conditions and are designed to establish quickly so that they are not blown away by the wind to unwanted locations.

The carrier may be mineral or vegetable.

And preferably organic or inorganic powders with high bulk density, low surface area, and low liquid adsorption. Preferred carriers are micaceous talcs,
pyrophyllite, dense kaolin clay, tobacco dust
-st), and crushed calcium phosphate rock.

The usability of the powders is optionally improved by the use of liquid or solid ionic, anionic or nonionic wetting agents. Preferred wetting agents include alkylbenzenes and alkylnaphthalene sulfonates, fatty alcohol sulfates, amines or acid amides, long acid esters of sodium isothiones, esters of sodium sulfosaxonate, and sulfated or sulfonated fatty acid esters. These include petroleum sulfonates, vegetable oil sulfonates, and tertiary acetylene glycols. Dispersants are also useful in this powder composition.

Typical dispersants include methyl cellulose, polyvinyl alcohol, lignin sulfonate, alkylnaphthalene sulfonate polymers, sodium 7-talene sulfonate, polymethylene bisnaphthalene sulfonate, and sodium N-methyl-N-(long chain [1) taurate. There is.

Inert adsorbent grinding aids are often used as auxiliaries in the production of coarse powders. Preferred crushing cuttings include butano2lugite clay, diatomaceous silica,
Synthetic #fine silica, synthetic calcium or magnesium silicate, etc. are available.

In typical powder compositions, the carrier usually has a molecular weight of 30 to 90%.
Ff-shoat at # degree of weight %. Grinding aid is usually 5-50M
% and wetting agent up to about 1.0% by weight. Dispersants, if present, may be present up to about 0.5% by weight, and small amounts of anti-caking agents and anti-static agents may also be present. The particle size of the entire composition is typically about 30-50 microns.

B. Solution The aqueous solution of the active substance is approximately 1 to 200 ron/neeker (
A solution of approximately 9 to 1875 t/ha) is prepared to provide the required amount of active ingredient. A gourmet non-toxic surfactant, usually 0.05-0.5% gold, is added to completely improve the wettability of the solution and to ensure good dispersion on the plant surface.

Anionic, cationic, nonionic and zwitterionic surfactants can all be used for this purpose.

In terms of economy and convenience of use, liquid compositions using water are preferred.

Suitable anionic surfactants include c.

~8. Examples include aliphatic alcohol 7-ethyl alkali metal, ammonicum, amine salts, and sodium salts of C9-1, alkylbenzene sulfonates. Suitable cationic surfactants include C8-1. There are dimethyldialkyl quaternary ammonium halides with alkyl chains. Suitable nonionic surfactants include C
IG~, polyoxyethylene adduct of 8 aliphatic alcohol, C6~1. A polyethylene oxide condensate of alkylphenol having an alkyl chain, a condensation product of 5 to 25 moles of ethylene oxide to alkylphenol,
There are sorbitan esters condensed with 10 to 40 moles of ethylene oxide. Suitable ampholytic surface active compounds include one C8-5. There are secondary and tertiary aliphatic amines having anionic water solubilizing groups such as aliphatic groups tosulfates and sulfonates. For example, SoP Umu 3
-door' fluaminoglobionate and sodium chloride sulfonate. Suitable zwitterionic surfactants include aliphatic quaternary ammonium compounds having 08-18 aliphatic groups and anionic water solubilizing groups. For example, 3 (N t N-dimethyl-N-hexadecyl ammonio)propane-1-
sulfonate, and 3~(N,N,-tumethyl-N-
hexadecyl ammonio)-2-hydroxypropane-
1-sulfonate and the like.

C1 Emulsifiable Concentrates Emulsifiable concentrates are solutions in which the active substance and emulsifier are dissolved in a water-immiscible solvent. Prior to use,
This is diluted with water to form an emulsion in which the solvent droplets are dispersed.

A suitable solvent is weed oil.
l), chlorinated hydrocarbons, water-immiscible esters, ethers, and carbon atoms. Typical emulsifiers include anionic or nonionic surfactants or mixtures thereof. For example, long-chain mercaptan polyethoxy alcohol, alkylaryl polyethoxy7 alcohol, sorbitan aliphatic ester, ether of sorbitan aliphatic ester and polyoxyethylene, ester of fatty acid or rosin acid with polyoxyethylene glycol, aliphatic alkylol These are amide condensates, calcium or amine salts of aliphatic alcohol sulfates, oil-soluble petroleum sulfonates, or mixtures of these emulsifiers. These usually comprise about 1 to 10% by weight of the total composition.

A typical emulsifiable concentrate contains about 15-50% active material, about 40-82% solvent, and about 1-10% emulsifier.

Other additives may also be included, such as amending agents and clarifying agents.

D. Wettable powder Wettable powder contains the active substance, an inert solid Efste/Gu,
Solid extenders are natural substances and some are synthetically obtained. Suitable surfactants may include, for example, kaolinite, atano or lugite clay, montmorillonite clay, synthetic silica, synthetic magnesium silicate and calcium sulfate dihydrate, nonionic and anionic surfactants, wetting agents, etc. and as a dispersant. Usually includes one or the other.

Preferred wetting agents are 2, alkylbenzenes and alkylnaphthalene sulfones), sulfates of JIl[/S alcohols, amines or acid amides, long chain acid esters of sodium isothionate, esters of sodium sulfosuccinate, esters of fatty acids. These include sulfates or sulfonates, petroleum sulfonates, sulfonated vegetable oils, and sulfuric acid glycols. Preferred dispersants include methyl cellulose, polyvinyl alcohol, lignin sulfonate, polymerized alkylnanthalene sulfonate, sodium naphthalene sulfonate, polymethylene bisnaphthalene sulfonate, sodium chloride N-methyl A, -N (long chain) taurate 7Z horse chestnut.

A typical wettable powder contains 25-90% active material, 0.
5-2.0% wetting agent, 0.25-5.0% dispersing agent,
It contains 9.25-74.25% of inert extension. Antifoaming agents and corrosion inhibitors can also be used in place of extenders, often on the order of 0.1 to 1.0%.

E. General Generally, coupled agricultural compositions for post-emergence applications can be used, including conventional powder cloths and spray equipment. The t#-i, herbicidally effective amount or growth-regulating effective amount of the active substance that is effective for obtaining the desired result varies depending on the class of the target plant and the main conditions. Herbicidal effect is permeable to the skin, 0.1~
Fifty pounds of active ingredient/naker is achieved, preferably 1-10. On the other hand, Plant Growth Control ifJ Yorai has 1 post and 0
．． 1 to 20 lbs. of active ingredient/knicker, preferably 0.
Achieved in 5-5.

Agent Patent Attorney Hideaki Kurihara

Claims (1)

[Claims] 1. A compound of aluminum N-phosbomethylglycine. 2. The compound of claim 1, wherein the molar ratio of aluminum to acid anion is substantially 4:1. 3. The compound of claim 1 in substantially hydrated form. 4 Herbicidal compositions of aluminum N-phosphonomethylglycine mixed with at least one inert carrier. 5 Herbicidal effective amount of aluminum N-phosphonomethylglycine can be added where gold is desired to control unwanted plant growth including gold? How to adjust. 6. A method of controlling unwanted plant growth comprising adding a herbicidally effective amount of a mixture of aluminum N-phosphonomethylglycine and at least one inert carrier to the location where control is desired. 7. For use as a herbicide or plant growth regulator, comprising an effective amount of an aluminum compound of N-phosphonomethylglycine and at least one additive in which the molar ratio of aluminum to acid is substantially 1:4. m acid. 8 N-phosphonomethylglycine and aluminum compound An aluminum N-phosphonomethylglycine compound prepared by heating to reflux temperature in the presence of gold water, cooling, filtering, and concentrating the filtrate. 9. The compound according to claim 8, wherein the aluminum compound is aluminum hydroxide. 10. The compound according to claim 8, wherein the aluminum compound is aluminum isoglopoxide.