JPS6145638B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula () A novel compound represented by [wherein, R represents hydrogen or a methyl group, the carbon marked with * is an asymmetric carbon, and the carbon marked with ** is an asymmetric carbon when R is a methyl group], Regarding its manufacturing method and uses. More specifically, the present invention relates to L- or DL-2-amino-4-methylphosphinobutyryl-glycine or L- or DL as a new compound.
-2-Amino-4-methylphosphinobutyryl-
This invention relates to L-alanine or a salt thereof. The present invention also relates to the general formula () A compound represented by [R ₁ is an amino protecting group, R ₂ is a phosphate protecting group] or its active carboxylic acid derivative and the general formula () [R is hydrogen or methyl group, R ₃ is hydrogen or carboxylic acid protecting group] is reacted to form the general formula () [In the formula, R, R ₁ , R ₂ , and R ₃ have the same meanings as above] is produced, and then each of the amino group, carboxylic acid group, and phosphoric acid group of the compound is This invention relates to a method for producing a compound of general formula () by removing any remaining protective groups. Furthermore, the present invention cultivates microorganisms belonging to the genus Streptomyces under aerobic conditions and contains the general formula (') in the culture solution. Regarding a method for producing a compound of general formula ('), which is characterized by accumulating and collecting the compound represented by, and containing at least one of the compound of general formula () and its salt as an active ingredient. This invention relates to herbicides and agricultural fungicides, which are characterized by: It was known that 2-amino-4-methyl-phosphinobutyric acid and N-(2-amino-4-methylphosphinobutyryl)-L-alanyl-alanine have herbicidal and antifungal effects (JP-A-Sho 48−
No. 82028, No. 49-14644, No. 49-14644, No. 52
-139727 and pending application by the present inventors).
As a result of further research, the present inventors obtained a new compound of the general formula () (hereinafter referred to as the present compound), and learned that this compound has strong herbicidal activity and an action as an agricultural fungicide. I have completed my invention. L- or D・L-2- of the formula () used as a raw material in the method of the present invention shown in FIG.
Amino-4-methylphosphinobutyric acid was disclosed in Japanese Patent Application Laid-Open No. 1973-
85538, 48-91019, and 49-31890. In carrying out the second method of the present invention, the present compound is obtained by coupling 2-amino-4-methylphosphinobutyric acid and glycine or alanine according to the general method of peptide synthesis. That is, 2-amino-4-methylphosphinobutyric acid with a protected functional group, for example, the formula (a) The compound represented by the general formula (a) is coupled with a commercially available methyl ester of glycine or alanine (a) by a mixed acid anhydride method. A compound represented by the formula [wherein R is hydrogen or methyl] is obtained, the benzyloxycarbonyl group is removed by catalytic reduction, and the compound of the general formula () is produced by saponification with an alkali. Examples of amino-protecting groups in the compound of general formula () include aralkyloxycarbonyl groups such as benzyloxycarbonyl groups and trifluoroacetyl groups, as well as amino-protecting groups known for peptide synthesis. As protecting groups, ester-forming groups such as methyl ester, t-butyl ester and the like, especially alkyl groups, can be used. General formula ()
In condensing the compounds () and (), in addition to the mixed acid anhydride method described above, the use of a dehydrating agent such as DCC, or the method of active carboxylic acid derivatives such as acid halide can be used. The reaction temperature is usually cold or room temperature, the reaction solvent is an inert organic solvent capable of dissolving the reaction reagents, and the reaction time is 1 hour to 1 night. To isolate the compound of the general formula () from the reaction solution, the usual amino acid peptide separation method can be applied, but it is preferable to use an ion exchange resin.After neutralizing with a weakly acidic ion exchange resin, it is first neutralized with a strongly acidic ion exchange resin. After adsorption to a resin, the compound is eluted with dilute alkaline water, and the ninhydrin-positive and neutral fractions are collected and concentrated to dryness to obtain the present compound as a white powder. This compound has one asymmetric carbon when R is hydrogen,
When R is methyl, it has two asymmetric carbon atoms, both of which are L-type or D/L-type coordination. N-(2-amino-4-methylphosphinobutyryl)-L-alanine (') can also be produced by microbial fermentation. That is, the third
The strain of Streptomyces used in the method of the present invention has the ability to produce a sufficient amount of N-(2-amino-4-methylphosphinobutyryl)-L-alanine to be collected in the culture. What you have is used. As such Streptomyces, a strain isolated from soil by the present inventors, identified and named Streptomyces hygroscopicus (strain number SF-1293) can be used. This Streptomyces hygroscopicus SF
-1293 (This bacterium was originally deposited with the National Institute of Micro-Technology on June 25, 1971 as the National Institute of Micro-Technology Deposit No. 996, and was subsequently deposited under the Budapest Treaty on May 19, 1981. No. 130, transferred and deposited as FERM BP-130) is a known bacterium, and its mycological properties are described in the inventors' patent No. 82-7768 (Japanese Patent Publication No. 51-639).
It is stated in the official gazette. Strain SF-1293, as seen in the case of other strains of the genus Streptomyces, is susceptible to changes in its properties, and can be mutated by artificial mutagenic means using, for example, ultraviolet rays, X-rays, radio frequencies, radiation, chemicals, etc. Even with such a mutant strain, N-
(2-amino-4-methylphosphinobutyryl)-
Any Streptomyces strain capable of producing L-alanine can be used in the method of the present invention. In the third method of the present invention, strain SF-1293 is cultured in a medium containing nutrients that can be used by common microorganisms. As the nutrient source, any known nutrient source conventionally used for culturing Streptomyces bacteria can be used. For example, glucose, starch, glycerin, sucrose, starch syrup, molasses, etc. can be used as carbon sources. Also, soybean flour, wheat germ, meat extract, peptone, dry yeast, cornstarch liquor, ammonium sulfate, sodium sulfate, etc. can be used as the nitrogen source. Calcium carbonate, salt, etc. as necessary.
In addition to adding inorganic salts such as potassium chloride and phosphate, appropriate organic and inorganic substances are added that help the growth of bacteria and promote the production of N-(2-amino-4-methylphosphinobutyryl)-L-alanine. You can. As for the culture method, the liquid culture method, especially the deep culture method, is most suitable, as is the case with general antibiotic production methods. Cultivation is carried out under aerobic conditions, and the appropriate temperature for cultivation is 25 to 35 degrees, but in many cases
Culture at around 28℃. Thus, the production of N-(2-amino-4-methylphosphinobutyryl)-L-alanine reaches its maximum in 3 to 5 days in both shaking culture and tank culture. Generally used physicochemical methods can be used to collect the active ingredient from the culture solution. N-(2-amino-4-methylphosphinobutyryl)-L-alanine mainly exists in the liquid part of the culture, but since it is a water-soluble amphoteric substance, when extracting and purifying it, Amberlite IR was used. −
120, cation exchange resin such as Dowex 50W or Amberlite IRA-400, IR-45, IR-
Adsorb it using an anion exchange resin such as 4B,
This can be eluted using a suitable acid, alkali or salt solution. For example, there is a method in which the culture solution is passed through a Dowex 50W (H type) resin tower, the active ingredients are adsorbed to the resin part, and then eluted with aqueous ammonia.
Amino-4-methylphosphinobutyryl)-L-
This is an effective method for purifying alanine. N-(2-amino-
The crude powder of 4-methylphosphinobutyryl)-L-alanine can be further purified by chromatography using cellulose, silica gel, alumina or Sephadex. The N-(2-amino-4-methylphosphinobutyryl)-L-alanine thus obtained is a white amorphous powder. The obtained compound () is novel and has a herbicidal action and a bactericidal action for agricultural and horticultural purposes. Herbicides and agricultural and horticultural fungicides containing salts, chelates, esters, or amides as active ingredients. That is, in terms of herbicidal activity, this compound has an annual herbicidal effect;
It is effective in killing perennial weeds and bushes, and can be used from the time of weed and bush germination to before, during, or after the growing season. It is characterized by being spacious. This compound is effective against almost all kinds of weeds, including annual weeds such as Japanese field weed and Japanese grasshopper;
It exhibits a particularly strong killing effect when sprayed on the stems and leaves of perennial weeds such as Aedes japonica and japonica grass, as well as miscellaneous shrubs such as Kumai strawberry and beech. The herbicidal activity of this compound is characterized by not only a contact effect but also a strong systemic transfer type effect, which is particularly effective in preventing the regeneration of perennial weeds that actively propagate vegetatively from underground. One of the characteristics of this compound is that it can be applied to weeds in the fall and used to prevent germination in the spring of the following year.For example, when treated with the leaves and stems of Cyperus japonica in the latter stages of growth, it is transferred into the body of the cypress, and is used to prevent germination in the spring of the following year. It accumulates in tubers and prevents them from sprouting. Furthermore, this compound can also be applied to aquatic plants. Specifically, it is effective against plants that float on the water surface such as duckweed and water hyacinth, plants that float in the water such as diatoms, and plants that have roots on the bottom of the water such as Japanese pine and Japanese sardine. Excellent effects can be obtained by adding this compound. In particular, water hyacinth, a problem weed, shows excellent effects in killing and preventing regeneration when sprayed on the stems and leaves. The present compound, which has the excellent characteristics described above, is suitable for an extremely wide range of uses as a herbicide.
In other words, in agricultural land, when used before sowing crops,
This compound kills weeds and is quickly inactivated in the soil, so it does not harm crops. After harvesting in fields and paddy fields, perennial weeds can be treated in the fall to prevent their occurrence in the spring of the following year. As mentioned above, this compound has a strong effect on almost all kinds of weeds and trees, which are useful forest trees.
Cypress has resistance. Therefore, it is suitable for underbrushing and weeding in cypress plantations. In addition, it has a strong effect on not only weeds but also shrubs and kills them, so it can be used as a herbicide for preparing the ground in afforestation areas. In addition to the above, it is extremely effective for weeding undergrowth in orchards, weeds and bushes in pastures, and on non-agricultural lands such as road shoulders, factory grounds, and cleared land. It is also suitable for controlling aquatic plants in lakes, waterways, irrigation, etc. The amount of this compound required to kill annual weeds, perennial weeds, and shrubs and prevent their regrowth varies depending on climatic conditions such as temperature and light intensity.
It is used in the range of 10g to 2000g per are. This compound is also useful as an agricultural and horticultural fungicide when used at a lower concentration than that used as a herbicide. For example, it shows excellent control effects against rice sheath blight or rice blast. Therefore, the concentration used in this case needs to be low enough to cause no phytotoxicity to rice, and it needs to be high enough to control rice blast or rice sheath blight. Specifically, when this substance is used as a liquid agent, the concentration of this substance in the spray liquid is 5 to 5.
50 ppm (assuming that 100 sprays per 10 ares after spraying, the amount of the drug per 10 ares is 0.5 to 5 g) is appropriate, and in the case of powders, it is desirable to contain this substance in the range of 0.1 to 1.0%. In preparing the present compound, preparations such as aqueous solutions, wettable powders, emulsions, etc. can be used in addition to powders and fine powders. When implementing these preparations, octylphenyl polyoxyethanol, polyoxyethylene dodecyl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl allyl ether, etc. are used to improve spreadability, adhesion, and dispersibility. It is possible to increase the certainty and increase of the effect by adding a surfactant. In addition, this compound can be used in the form of a free acid or its salt. When the compound is in the form of a salt, it may contain, for example, alkali metals such as sodium, potassium, lithium, alkaline earth metals such as magnesium, calcium, copper, zinc, nickel, manganese, etc. Salts with metals (acid acids): Salts with amines such as ammonium, mono-, di- and tri-lower alkylammonium, mono-, di- and triethanolammonium, mono-, di- and tri-lower alkylene ammonium; hydrochloric acid, sulfuric acid, odor Salts with one or more mineral acids such as hydrohydric acid, phosphoric acid, perchloric acid, nitric acid, or organic acids such as acetic acid, propionic acid, citric acid, tartaric acid, monochloroacetic acid, trichloroacetic acid, and trifluoroacetic acid ( It can be in the form of an acid addition salt) or a chelate. The present compound may also be used in herbicides and agricultural and horticultural fungicides in the form of esters, especially lower alkyl esters, or in the form of acid amides with lower alkyl amines. Next, the present compound will be specifically explained using reference examples, working examples, and test examples, but the present invention is not limited to the following examples and test examples. Reference Example 1 (a) Dissolve 4 g of L-2-amino-4-methylphosphinobutyric acid in 20 ml of water, add 8 ml of 5N aqueous sodium hydroxide solution, and stir under ice cooling. A mixture of 25 ml of a toluene solution (manufactured by Tokyo Kasei Kogyo) containing 30 to 35% carbobenzoxy chloride and 10 ml of a 5N aqueous sodium hydroxide solution is added to this in 5 portions over 30 minutes. After stirring at room temperature for 1 hour, about 20 ml of a mixture of carbobenzooxychloride reagent and alkali having the above composition was added several times, and the mixture was stirred for 2 hours. After the reaction is complete, separate the aqueous layer, wash twice with 40 ml of ethyl ether, and discard the ethyl ether layer. 40 ml of ethyl acetate in the aqueous layer
Add 6N hydrochloric acid to adjust the pH to 1-2. After shaking well, the ethyl acetate layer is separated, and the aqueous layer is further extracted with the same amount of ethyl acetate. The ethyl acetate layers are combined, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a colorless syrup-like substance. Dissolve it in a small amount of ethyl acetate, add ethyl ether, and let it stand at room temperature to crystallize. Separately, 5.5 g of white crystals are obtained. Dissolve 1.5 g of this substance in 10 ml of methanol, then add an ether solution of diazomethane until the liquid turns yellow. Concentration under reduced pressure yields about 1.6 g of a colorless syrup-like substance. The molecular weight of this substance according to mass spectrometry is 343 and the formula: This is a compound represented by (b) Dissolve this in 50 ml of 0.5N sodium hydroxide-methanol solution and stir well for 1 hour in a water bath at 50°C. After neutralizing the reaction solution with 2N hydrochloric acid, methanol is distilled off, the residue is dissolved in about 30 ml of water, and the pH is adjusted to 2 with 2N hydrochloric acid. HP-
20 resin (manufactured by Mitsubishi Chemical Industries) column (1.2 cm x
After washing with 100 ml of water, elute with methanol. Approximately 30 ml of the eluent fraction exhibiting ultraviolet absorption is collected and concentrated to yield approximately 1.4 g of a colorless syrup-like substance. If this substance is dissolved in a small amount of chloroform and left to stand, it will crystallize. The molecular weight determined by mass spectrometry is 329, and the obtained formula is formula (a). This is a compound represented by Example 1 (a) 1 g of compound (a) described in Reference Example 1 (b) is dissolved in 12 ml of tetrahydrofuran, 0.45 ml of triethylamine is added, and after cooling to 0°C, 0.41 ml of isobutyl chloroformate is added and shaken well.
To this was added 0.8 g of L-alanine methyl ester hydrochloride (manufactured by Tokyo Kasei) dissolved in 5 ml of chloroform containing 0.5 ml of triethylamine. Stir for 30 minutes at 0°C, leave overnight at room temperature, and concentrate to obtain a syrup-like substance. Dissolve this in 70 ml of chloroform and remove the chloroform layer with 10 ml of 0.5 mol sodium bicarbonate solution and 10 ml of 0.5 mol citric acid solution.
Wash twice with 10 ml of water and 10 ml of water. The chloroform layer was dehydrated with anhydrous sodium sulfate and concentrated to 1.2
A pale yellow syrup of g is obtained. The molecular weight of this substance according to mass spectrometry is 414, and it is a compound represented by the general formula (a) (where R is a methyl group). (b) To eliminate the benzyloxycarbonyl group by catalytic reduction, dissolve this substance in 25 ml of ethanol, add 2 ml of acetic acid and 300 mg of platinum oxide, saturate with hydrogen, and stir at room temperature for 3 hours. After the reaction is complete, the platinum oxide is separated and the liquid is concentrated under reduced pressure to obtain 1.1 g of a colorless syrup-like substance. Next, in order to remove the methyl group of the carboxylic acid phosphate protecting group, use this product.
Dissolve in 30 ml of 0.25N aqueous sodium hydroxide solution and stir in a water bath at 50°C for 1 hour to hydrolyze.
After finishing, add about 20ml of Amberlight IRC-50 (H ⁺ )
In addition, neutralize. After concentrating to about 10 ml, add strong acidic ion exchange resin Dowex 50W x 2 (H ⁺ , 200 ~
400 mesh) column (2 cm x 11 cm). After washing with 200 ml of water, eluting with 0.25 N sodium hydroxide aqueous solution, ninhydrin reaction was observed in the 3rd and 4th tubes in the 10 ml fraction (PH7.2), so when these were collected and concentrated, about 400 mg of 1 of this compound was obtained. A white powder of N-(2-amino-4-methylphosphinobutyryl)-alanine was obtained. Melting point 175-180℃ As monosodium salt C ₈ H ₁₆ N ₂ O ₅ P, Na (MW, 274) Calculated value C, 34.85, H, 5.82, N, 10.18% Experimental value C, 34.33, H, 5.60, N , 10.65% When this compound was developed on a thin layer of silica gel in a system of n-butanol-acetic acid-water (2:1:1), it showed a single spot that was positive for ninhydrin reaction.
Shown in Rf0.09. The infrared absorption spectrum of this compound is shown in FIG. Example 2 (a) By the same method as described in Example 2 using 800 mg of compound (a) described in Reference Example 1(b) and 0.45 g of glycine methyl hydrochloride, 1 of the present compound was prepared.
320 mg of white powder of N-(2-amino-4-methylphosphinobutyryl)-glycine was obtained. Melting point 152-157℃ As monosodium salt C ₇ H ₁₄ N ₂ O ₅ P, Na (MW, 260) Calculated value C, 32.32, H, 5.39, N, 10.79% Experimental value C, 31.53, H, 5.65, N , 10.24% When this compound was developed on a thin layer of silica gel in a system of n-butanol-acetic acid-water (2:1:1), it showed a single spot that was positive for ninhydrin reaction.
Shown in Rf0.08. The infrared absorption spectrum of this compound is shown in FIG. Example 3 Streptomyces hygroscopicus strain SF-1293 (Feikoken Jokyo No. 130) was cultured at 28°C for 8 days on lees-yeast extract agar, and the resulting spores were precultured. Medium (2.0% starch, 1.0% peptone, 0.3% meat extract, 0.05% dipotassium phosphate, PH7) 500
ml was inoculated. This was cultured with shaking at 28°C for 20 hours.
Further, the culture was subcultured into the same medium 20 and cultured with aeration at 28°C for 20 hours, and this was used as the seed mother of the main fermenter.
Glucose 1.0 in this fermentation using 300 tanks
%, starch syrup 4.0%, soluble vegetable protein 0.5%, soy flour
2.5%, yeast extract 0.2%, iron sulfate 0.001%, nickel chloride 0.001%, cobalt chloride 0.0001%, soybean oil
Production medium 200 with a composition of 0.3% (PH7) was inoculated with the above seed mother at a rate of 5%, and cultured with aeration at 28°C for about 96 hours. The obtained culture solution is filtered at pH 3.0, 150% of the solution is passed through a column (7.5) filled with activated carbon, and then washed with 30% of water. This passing liquid and washing liquid were combined (180, PH3) and Diaion SK-102S
(H ⁺ ) is applied to the resin column (9) to adsorb the active ingredients. After washing the resin tower with water, elute with 0.05N ammonia water. After concentrating the active fraction (PH5.5), it was applied to a Dowex 1×2 (acetic acid type) resin column (2.5), washed with water, eluted with 0.1N acetic acid, and the active fraction was concentrated to dryness to obtain N-(2 5.2 g of a crude powder containing -amino-4-methylphosphinobutyryl)-alanine was obtained. After suspending this product in 20 ml of water and removing water-insoluble white crystals, the aqueous solution was adjusted to pH 3.0 with formic acid, and a column (4 x 50 cm) packed with Dowex 50W x 2
and developed with 0.1N pyridine-formic acid (PH2). After removing the N-(2-amino-4-methylphosphinobutyryl)-alanyl-alanine that flows out first, the fraction containing N-(2-amino-4-methylphosphinobutyryl)-alanine is collected. The mixture was concentrated to dryness to obtain 550 mg of pale yellow powder. Dissolve this in a small amount of water, adjust the pH to 7 using N-caustic soda, precipitate it by adding an excess of ethanol, separate the precipitate, and dry it to obtain N-(2-amino-4-methylphosphide). 420 mg of inobutyril-alanine sodium salt was obtained. Melting point 175-180
°C, amino acid analyzer (manufactured by JEOL Ltd., JLC-6AH)
retention time 35 min with (N-(2-amino-4
The retention time of -methylphosphinobutyryl)-alnyl-alanine was 34 minutes. Example 4 Wettable powder N-(2-amino-4-methylphosphinobutyryl)-alanine choline 5% polyoxyethylene alkyl phenyl ether
8% diatomaceous earth 87% or more are mixed uniformly and ground finely. Before use, dilute with water and spray. % is by weight. Same Example 5 Water solvents N-(2-amino-4-methylphosphinobutyryl)-glycine/choline 5% polyoxyethylene alkyl ether 8% water 87% or more are mixed and dissolved. Before use, dilute with water to a specified concentration and spray on plants. Example 6 Powder N-(2-amino-4-methylphosphinobutyryl)-sodium alanine 0.5% Calcium stearate 0.3% Talc 99.2% or more are uniformly mixed and ground. When using, spray 3 to 4 kg per 10 ares onto plants. Next, some test examples regarding the efficacy of this substance as a herbicide and agricultural fungicide are shown. Test Example 1 The following plants were tested with this compound shown in Table 1.
The 0.1% or 0.2% solution was sprayed on 150 leaves per 10 are. As a surfactant, octylphenyl polyoxyethanol was added at a concentration of 0.1%. The investigation was carried out on the mortality index (0: harmless, 5: withering) on the 21st day after treatment, and the regeneration suppressing effect (-: no regeneration, +++: maximum regeneration) 3 months after treatment.
I followed him. Plant names in Table 1 are indicated by symbols as follows. A: Novieum, B: Japanese grasshopper, C: Thrush, D: E: Mugwort, F: Japanese commonweed, G: Water hyacinth, H: Japanese silverwort, I: Chigaya, J: Japanese pampas grass, K: Cypress, L: Japanese blackberry, M: Japanese cypress, N: Japanese sagebrush

【table】

[Table] Test Example 2 The minimum inhibitory concentration of this compound against various plant pathogenic microorganisms was measured. The plant pathogenic filamentous fungi and test bacteria shown in Table 2 below were tested using the agar dilution plate method. That is, the present compound is mixed into a Tzapek agar medium to a predetermined concentration, poured into a shear plate, and allowed to solidify.The surface is then inoculated with the test bacteria, and after culturing at 28°C for 3 days, the presence or absence of bacterial growth is determined. Observations were made to determine the minimum inhibitory concentration (ppm). The results are shown in Table 2.

[Table] Test Example 3 Control test against rice blast disease A predetermined concentration prepared by the same method as in Example 4 was applied to four-leaf stage paddy rice seedlings (variety: Jukoku) grown in clay pots with a diameter of 9 cm. After spraying the reagent, spray it on a turntable at a rate of 35 ml/2 pots using a spray gun (2 Kg/cm ² ), and after air-drying, place it in a humid room at 25°C to remove spores of the rice blast fungus. The suspension was spray inoculated. Five days after inoculation, the number of lesions per leaf was investigated, and the control value was calculated according to the following formula. Control value (%) = (Number of lesions per leaf in untreated area) - (Number of lesions per leaf in treated area) / Number of lesions per leaf in untreated area x 10
0

[Table] The control drug contains O-ethyl-S as an active ingredient.
A commercially available fungicide (trade name: Hinozan Emulsion) containing 30% S-diphenyldithiophosphate was used. Test Example 4 Control test against rice sheath blight A test chemical at a predetermined concentration prepared by the same method as in Example 4 was applied to 7-leaf stage rice plants (variety: Jukoku) grown in clay pots with a diameter of 9 cm. Using a spray gun (2Kg/cm ² ), the spray solution was sprayed on a turntable at a rate of 35ml/2 pots, and after air-drying, rice prints were cultured on a potato decoction agar medium for 48 hours. Bacterium blight was inoculated by punching out mycelium along with agar using a cork borer with a diameter of 5 mm, and inserting one piece per stem into the leaf sheath, and placing it in a humid room at 30°C for 5 minutes.
After a day, the lesion length per stem was measured, and the control value was calculated according to the following formula. Control value (%) = (lesion length per stem in untreated area) (lesion length per stem in treated area) / lesion length per stem in untreated area x 100

[Table] The control drug contains validamycin as an active ingredient.
A commercially available fungicide (trade name: validamycin solution) containing A3% was used.

[Brief explanation of the drawing]

Figure 1 shows N-(2-amino-4-methylhoffuinobutyryl)-alanine, Figure 2 shows N-(2-
FIG. 2 is an infrared absorption curve diagram of amino-4-methylphosphino-butyryl)-glycine measured in a potassium bromide tablet.

Claims (1)

[Claims] 1 General formula () A phosphorus-containing compound or a salt thereof, wherein R is hydrogen or a methyl group. 2 General formula () A compound represented by [R ₁ is an amino protecting group, R ₂ is a phosphate protecting group] or its active carboxylic acid derivative and the general formula () [In the formula, R is hydrogen or a methyl group, R ₃ is hydrogen or a carboxylic acid protecting group] is reacted to form the general formula () [In the formula, R is hydrogen or a methyl group, R ₁ is an amino protecting group, R ₂ is a phosphoric acid protecting group, and R ₃ is hydrogen or a carboxylic acid protecting group] is produced, and then from this compound an amino protecting group, A method for producing a phosphorus-containing compound represented by the general formula (), which comprises removing a carboxylic acid protecting group and a phosphoric acid protecting group. 3. Culture bacteria that produce the following compound belonging to the genus Streptomyces under aerobic conditions, and extract the general formula (') from the culture solution. A phosphorus-containing compound represented by N-(2-amino-4-
A method for producing the new antibiotic N-(2-amino-4-methylphosphinobutyryl)-L-alanine, which comprises collecting methylphosphinobutyryl)-L-alanine. 4 General formula () A herbicide and a sterilizer for agricultural and horticultural purposes, characterized by containing as an active ingredient at least one of a phosphorus-containing compound represented by the formula (wherein R is hydrogen or a methyl group), or a salt, chelate, ester, or amide of the compound. agent.