KR840000708B1 - The preparation for 2-amino-4-methyl-phosphinobutanoic acid choline - Google Patents

Abstract

The title compd. [MeP(O) (O-) (CH2)2CH(N+H3) CO2- Me3N+ (C-H2) 2OH was prepd. from choline and choline salts by treatment with aq. MeP(O) (OM1/n) (CH2)2CH(NH2)CO2H (II; M=H, metal atom; n=valency of M). 2-Amino-4-methyl-phosphinoyl butanoic acid choline (AMPB);I) controlled annual and perennial weeds, shrubs, and aquatic plants more effectively than II. Compns. contg. I are described.

Description

Preparation of 2-amino-4-methyl-phosphinoyl butyrate choline

1 is an infrared absorption spectrum of the product of Example 1 (L-2-amino-4-methyl-phosphinoylbutyrate choline).

2 is an infrared absorption spectrum of the product of Example 2 (DL-2-amino-4-methyl-phosphinoylbutyrate choline).

The present invention is the following formula (I)

It relates to a method for producing a compound represented by, namely 2-amino-4-methyl-phosphinoyl butanoic acid choline (hereinafter referred to as AMPB choline).

Formula (Ⅱ)

Among the compounds represented by [where R is a hydroxy group, M is a hydrogen atom or a metal atom such as Na, K, Ca, Ba, Mg, and n is the valence of M],

2-amino-4-methyl-phosphinoylbutyric acid is acid hydrolysis of (2-amino-4-methylphosphinobutyryl) -alanylalanine for its L-body (Japanese Patent Laid-Open No. 1973-85538) Alternatively, the inventors of the present invention have established the production method of the present invention either by enzymatic digestion (Japanese Patent Laid-Open No. 1974-31890) or by the synthesis method (Japanese Patent Laid-Open No. 1973-91019) for the DL.

These compounds represented by formula (I) are useful herbicides (Japanese Patent Application Nos. 1977-133014, 1977-157421, 1977-154722, 1977-158832 and 1978-36059), but the inventors have also studied and studied various effective derivatives. The present invention was completed by finding that the compound represented by the formula (I) has an extremely strong herbicidal effect.

The compound represented by the formula (I) of the present invention is produced by adding the equimolar amount of choline to the aqueous solution of the compound represented by the formula (II). Here, "choline" means choline and salts of choline (mineral acid, sulfuric acid, ginseng, etc.).

Referring to the present invention again, the compound represented by formula (I) is added equimolar choline to an aqueous solution of the compound represented by formula (II) (wherein M is a hydrogen atom) or formula (II) (wherein M is Na (K, Ca, Ba, Mg, etc.) is produced by adding equimolar amounts of the acid salts of choline (hydrochloric acid, sulfuric acid, phosphoric acid, etc.) to an aqueous solution of the compound. In the former case, since choline tends to form carbonates, it is preferable to use decarbonized water.

Next, the above aqueous solution is concentrated to dryness, and the residue is dissolved in a solvent such as 10 vol (methol) methanol and ethanol, and 40-50 vol. Of ethyl acetate, chloroform, benzene, ether, etc. is added to give a white precipitate. The white powder of the choline compound represented by Formula (I) can be obtained by drying this under reduced pressure in the presence of a drying agent.

In the latter case, inorganic salts are produced as by-products in the reaction solution, but when the inorganic salts are water-soluble, the compound of formula (I) is extracted with an alcohol or a mixture of alcohol and acetone from the residue of the reaction solution or (Iii) In the case of water solubility, for example, barium sulfate and the like are easily desalted by filtration and removal from the reaction solution.

The chemical properties of the compound represented by the formula (I) thus obtained (hereinafter abbreviated as the compound of the present invention) are shown in the first table.

[Table 1]

In addition, it was confirmed from the results of mass spectrometry and thin layer chromatography that the material produced by the above-mentioned treatment was a single substance and a compound represented by formula (I).

That is, as shown in Table 1, AMPB choline exhibits protonated molecular ion peak (M + 1) at m / e285 by field desorption masschromatomatometry, which indicates that AMPB choline Imply that it is a single substance.

Next, by cellulose thin layer chromatography of AMPB choline (developing solvent ethanol-mol 4-1), the ninhydrin reagent (AMPB and AMPB containing at FF 0.31 is blue-violet but no choline occurs) And Dalsport with two reagents, the dragendorff reagent (containing choline and choline, which occurs in reddish brown but does not develop AMPB), suggesting that choline is a single substance.

The compound of the present invention is absorbed when left for a long time, but is used as a herbicide in a stable form by various preparations such as liquids, powders, granules, and hydrating agents as described below. In recent years, not only non-agricultural, but also a lot of perennial weeds in rice fields, fields, orchards, grasslands, etc., which is a problem.

Perennial weeds have a living base in the lower parts such as rhizome, tuber, bulb, and root, and have many storage nutrients and strong regenerative germination.

Even if only the ground part is killed, new individuals are generated in the new subterranean ground. Therefore, if regeneration is not suppressed, perennial weeds are not prevented, and they have extremely strong drug resistance compared to annual weeds.

In agricultural land, the trophic propagation organs in the thin basement of these perennial weeds grow widely throughout the body by soil tillage, agitation, and migration.

As a perennial weed control agent, n-phosphonomethylglycine (hereinafter referred to as glyphosate) is known, but there is a weak point in light heat weeds, and a broad spectrum of herbicidal spectrum is required.

Bunge), 밤나무(Castanea Crenata Sieb or Zucc.), 까마귀밥나무(Japanese bush Cranberry, Viburnum dilatatum thunb.) 등 잡관목이다. 초목지에서도 그 주위에 잡관목이 발생하여 그 방제가 필요하다.In addition, control of lumps of wood is an important problem in non-agricultural land, grassland, and granulated land. In plantation, cedar, cypress, etc., compete for seedlings, light, and nutrients.

Bunge), chestnut (Castanea Crenata Sieb or Zucc.), Crowwood (Japanese bush Cranberry, Viburnum dilatatum thunb.) In the vegetation, a variety of trees appear around them, and their control is necessary.

A large number of herbicides have been developed to date, but few herbicides are effective for peduncles. It is different from herbaceous plants, and is difficult to penetrate the drug and has such an epidermis, so that even if the leaves fall off, the branches remain and grow again, and they are generally larger than herbaceous plants.

The compound of the present invention exhibits excellent herbicidal effect by the foliage treatment and soil treatment, but has a strong adhesive effect especially when the foliage treatment on annual weeds, perennial weeds and lumbers, and at the same time the current in the plant (轉 流) It has the property of killing the plant's growth point by transition, and has the excellent property as shown below.

In other words, by killing the annual weeds with strong regeneration, such as manna grass (cockspargrass), inhibits the regeneration, in the perennial weeds, the compound of the present invention treated in the foliage is based on the life base of the perennial weeds Underground currents are transferred to the underground, such as roots, tubers, diameters, diameters, and roots, to kill the underground.

As a result, it is extremely difficult for perennial weed control, and the most important underground regeneration can be suppressed by foliage treatment. In addition, among the conventionally known weeds, the compound of the present invention, which is effective for lycopene, has inherited and transferred to the end of the lychee tree, exhibiting a strong killing effect, and inhibiting its regeneration and recovery.

Regeneration inhibitory effect of weeds and shrubs by the compounds of the present invention is effective at lower concentrations than glyphosate and glyphosate is less effective against broadleaf weeds and shrubs, but the compound of the present invention is a useful tree almost except for cypresses. It is powerful against all kinds of weeds and shrubs, and the weed spectrum is wide.

The herbicidal activity of AMPB choline was compared with 2-amino-4-methyl-phosphinoyl butyrate monosodium salt and 2-amino-4-methyl phosphinoyl butyrate diethanol ammonium salt. Inhibitory effect is high together.

As in the examples, they are different from one another, but the strong ones are the regeneration inhibitory effect, for example, L-2-amino-4-methyl-phosphinoyl butyrate monosodium salt or L-2-amino-4-methyl-phosphinoyl. Compared to the butyric monodiethylammonium salt, L-AMPB choline is twice as strong as regenerative inhibitory force (Experimental Example 1).

One of the problems in weed control is that weed growth is most prominent, and the most need for herbicide spraying is summer. Therefore, it is difficult to choose individual blades during rainy seasons. Herbicides are often lost. One of the properties of the compound of the present invention is excellent in that it penetrates and absorbs in plants after foliage treatment, and thus has little effect by rainfall after treatment.

That is, it has excellent rain resistance. In addition, it is the treatment under low temperature because it has excellent penetration and absorption, and exhibits its characteristics even under conditions in which the late growth of the plant and the metabolism of the plant are lowered and the penetration and absorption are suppressed as in the autumn treatment.

The compound of the present invention having the above characteristics acts strongly on almost all kinds of perennial weeds, perennial weeds, and shrubs except for cypress, and the target outpost can be controlled, and their regeneration and recovery are possible. It is strongly suppressed and has extremely high practical value.

Suspension and mowing in plantation are heavy labor and the reduction of workers is a major problem.

Problems in plantation are mainly large perennial weeds and shrubs, or the compound of the present invention has a strong effect on these weeds or shrubs as described above is suitable for stopping the plantation.

Since it has no harm to cypress, which is a useful tree, it is used as a mowing in cypress plantation, so it has an extremely excellent effect as a selective herbicide.

In addition, the compound of the present invention is easy to formulate powder, fine particles and the like, and such formulation is common in forest land. The reason for this is that it is difficult to obtain water in plantation, and powder and fine powder are difficult to attach to coniferous plants such as cedar.

The compounds of the present invention can also be used for mowing not only cypress but also cedar and other planting plants by such preparations. At present, there are few herbicides which are effective for both weeds and shrubs.

As an example, 3,2,3,3-tetrafluoropropionate sodium salt has a weak effect on forest herbicides and groats, which have a great effect on pampas grass, bamboo grass.

Because of this, after control of the pampas grass and stalks, various kinds of trees such as raspberry, chestnut, and crow rice are generated and changed to other vegetation.

As a result, there is a next need to use a medicament that inhibits the growth of cross-trees.

The compound of the present invention strongly kills both weeds and shrubs, and inhibits the recovery of the regeneration over a long period of time, which is a breakthrough without such concern.

The compound of the present invention has a property of sustaining its effect over a long period of time in plants but relatively inactivating in soil.

For this reason, the compounds of the present invention are suitable because they can suppress weeds for a long time when used before sowing of crops in the field and do not harm the sown crops.

In addition, when grass is used in paddy fields as a perennial weed control and other fall treatment agents, the present invention, which has passed through the plant, inhibits regeneration in the underground of the following spring.

On the other hand, the characteristics of the compound of the present invention which is adsorbed on the soil surface and becomes inactive in the soil relatively quickly can be applied to orchards. In other words, even when used for controlling the weeds of orchards, the compounds of the present invention are absorbed from the roots of orchards and there is no fear of causing weakness. In addition to plantation and farmland, the present invention can be used for a wide range of applications.

In the vegetation, a variety of scrubs develops, so that swimming, fighting, and other weeds competing with the grass to feed the weeds not only reduce the quality of the milk but also thorns such as crows (toxic plants). Weeds cause injury to cattle and horses.

The compound of the present invention kills the weeds between grasses by spot treatment and suppresses its regeneration.

In addition, it exhibits excellent effects as a control agent for annual, perennial weeds and mixed trees in non-agricultural areas such as factory sites, railway tracks, parks, public facilities, river sites, dikes, highways, golf courses, cold lands and clearing areas. Aquatic weeds and algae can be killed by the treatment.

The amount of the compound of the present invention required for the inhibition of regeneration due to the weeding of the weeds and the shrubs depends on climatic conditions such as temperature and light intensity and the type of weeds, but the amounts of herbicides (components) are shown in Table 2 below.

[Table 2]

In the formulation of the present invention, preparations such as powders, granules, liquid preparations, and emulsions can be used. To carry out these preparations, surfactants such as octylphenyl polyoxyethanol, polyoxyethylene dodecyl ether, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene alkylaryl ether may be added to enhance electrodeposition, adhesion and dispersibility. Can increase the effect.

Next, the present invention will be described in detail with reference to Examples and Test Examples, but the present invention is not limited to the following Examples and Test Examples, unless the gist thereof is changed.

Example 1

L-2-amino-4-methyl-phosphinoyl butyrate choline 3.55 g of L-2-amino-4-methyl-phosphinoyl butyrate was boiled and dissolved in 50 ml of cooled water, and 2.38 g of choline was dissolved. Was added.

Then, the residue was concentrated to dissolve the residue in 50 ml of ethanol, and 500 ml of ethyl acetate was added to precipitate a white precipitate. The clear portion of the rise was removed by decantation and the precipitate was washed with ethyl acetate and dried under reduced pressure in the presence of phosphorus pentaoxide to give 5.4 g of white powder of L-2-amino-4-methyl-phosphinoyl butyrate choline. Got it.

Melting point: 175-178 ℃, Elemental analysis (%): C: 42.20, H: 8.83, N: 9.81, P: 10.98 ( molecular formula _{C 10 H 25 N 2 O 5} P as the theoretical value: C: 42.25, H: 8.86 , N: 9.85, C: 10.90) Infrared absorption spectrum: shown in FIG.

Example 2

DL-2-amino-4-methyl-phosphinoyl butyrate choline

2.4 g of DL-2-amino-4-methyl-phosphinoyl butyrate butyrate was dissolved in 25 ml of water, and 1.52 g of choline sulfate was added.

The resulting precipitate of barium sulfate was filtered off and the filtrate was concentrated. The residue was dissolved in 25 ml of ethanol, and 250 ml of acetone was added to precipitate a white precipitate. The clear portion of the upper layer was removed by decantation and the precipitate was washed with a small amount of acetone and dried under reduced pressure in the presence of phosphorus pentaoxide to obtain 2.75 g of white powder of DL-2-amino-4-methyl-phosphinoyl butyrate choline. Got it.

Melting point: 152-157 ℃, Elemental analysis (%): C: 42.18, H: 8.82, N: 9779, P: 10.97 ( molecular formula _{C 10 H 25 N 2 O 5} P as the theoretical value: C: 42.25, H: 8.86 , N: 9.85, C: 10.90) Infrared absorption spectrum: shown in FIG.

Example 3

The above was mixed and ground uniformly.

When used, the leaves were sprayed as is.

Example 4

The above was mixed uniformly and finely ground. When used, the leaves were treated with dilution with water. Next, the effect of the compound of this invention is demonstrated by a test example.

[Test Example 1]

About the native weeds during the growing season, the predetermined concentrations of the compounds of the present invention and the compounds listed in Table 3 were sprayed on the foliage at about 150 L per 10 ars. Surfactant was added to 0.1% octylphenyl polyoxyethanol. Investigations were conducted on 21 days after the treatment for the hunger index (0: harmless, 5: killing), and 2 months after treatment (A, B: see Table 3) or 4 months (other). Were examined for the maximal regeneration. The results are shown in the third table.

[Table 3]

[Test Example 2]

In the cypress plantation, the predetermined concentration of the compound of the present invention and the compound described in Table 4 was foliage treated at about 150 L per 10 ars.

Investigations were made on the hunger index (0: harmless, 5: dead) at 30 days and 3 months after treatment.

Cypresses were 50-70 cm high, chestnut trees about 50 cm tall, 50-90 cm tall, pampas grass 100 cm tall, and raspberry 70-100 cm high. The results are shown in the fourth table.

[Table 4]

[Test Example 3]

Compounds of the present invention and Table 5 were scattered on the foliage at about 150 L per 10 arbors in a mixed tree native habitat.

Surfactant was added to 0.1% octylphenylpolyoxyethanol.

: 재생극대)에 대해서 조사하였다. 그 결과는 제5표에 표시한다.Investigations were conducted on high killing activity (0: harmless, 5: killing) at 1 month after treatment, and on the 3 months after treatment.

: Regeneration maximal). The results are shown in Table 5.

[Table 5]

Claims (1)

2-amino-4-methyl of formula (I) characterized by reacting with an equimolar amount of choline (choline and choline mineral acid (phosphate, hydrochloric acid, sulfuric acid, etc.) salt) to an aqueous solution of the following formula (II) Preparation of phosphinoyl butyrate choline.

In the above formula, R is a hydroxyl group, M is a hydrogen atom or a metal atom of Na, K, Ca, Ba or Mg, n denotes the valence of M.

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