SU975712A1 - Phosphorous-containing choline derivatives exhibiting herbicidal activity - Google Patents

Abstract

NEW MATERIAL:2-Amino-4-methylphosphino-butyric acid choline (AMPB choline) and (2-amino-4-methylphosphino-butyryl)-alanylalaninecholine (SF-1293 choline) of formula I: (R is OH or alanylalanine residue). USE:Herbicides for annual and perennial weeds, and miscellaneous shrubs capable of killing foliages and underground parts, e.g. subterranean stems. PROCESS:An equimolar amount of choline is added to an aqueous solution of a compound of formula I (M is H, Na, K, Ca, Ba, or Mg; n is the valence of M) to give AMPB and SF-1293 cholines of formula I together.

Description

This invention relates to the chemistry of organophosphorus compounds, namely CH-P-fCHj), -CH-A n - bj u where A-CO-NH-CH-CO-NM-CH-n-0 or 1, which have herbicidal activity and can be used to destroy annual and perennial weeds, shrubs and aquatic plants. The use of K-phosphonomethylglycine as a herbicide is known. The closest to the proposed compounds in terms of structure and designation are C2- "u" iHo-4- (jOKCH) (methyl) -phosphinoyl butyryl Khalilanan (SF-1293) ci -form 2-amino-4- (oxy) (methyl) phosphinoylbutanoic acid (AMPS) 33, which is described by the general formula O cH P-cHaCHj-cH-coR (.P)

to the new phosphorus-containing choline derivatives of the general formula (CHj) CHjCHijOH where R is hydroxyl or residue-α-hshanylalanine, M is hydrogen, sodium, calcium, barium and magnesium; n is the valence of the metal. However, these compounds exhibit an insufficiently high herbicidal activity. The purpose of the invention is to expand the range of herbicides and increase their activity. The goal is achieved by matching general formula I), which are herbicidal. activities that transform the activity of known herbicides. Compounds of general formula X1) are obtained by the interaction of choline and / or inorganic choline salt with 2-amino-4 (oxy) (methyl) -phosphonoylbutyryl) alanylalanine and / or 2-amino-4- (oxy) ( methyl) -phosphinoyl butanoic acid and / or its salt. The compounds described by the general formula (T) possess the physicochemical properties shown in Table 1. The structure of the obtained compounds was confirmed by mass spectrometer methods and thin layer chromatographic analysis. AMPV choline gives a protonated molecular ion peak (M + l) - at P1 / e 285 using the field desorption method with mass-chromatometry, which confirms that AMPV cholene is a single substance. AMPB choline gives a single spot with an R value of 0.31 in thin layer chromatography on cellulose (development solvent: ethanol / water 4: 1), when used for spot detection reagents with ninhydrin and Draggendrf, which shows that AMPB is em a single connection. The combination of AMPB and the compound containing AMPV gives a color reaction with ningrin, which develops blue-violet & the color, while non-AMPB compounds do not give this color reaction. Similarly, choline and choline-containing substances give a color reaction with the Draggendorf reagent, in which a reddish-brown color develops, while AMPB does not give a color reaction. Example. Choline L-AMPB. 3.55 g of L-AMPB is dissolved in 50 ivu of boiled and cooled water and 2.38 g-choline is added to the mixture. The mixture is concentrated and the residue obtained is dissolved in 50 ml of ethanol. A white precipitate is isolated by adding 500 ml of ethyl acetate .. The upper layer is discarded by decantation and the precipitate is washed with a small amount of ethyl acetate and dried in vacuum over phosphorus pentoxide to obtain 5.4 g of choline L-AMPB in the form of white powder melting at 175-178 Results of elemental analysis,%: Found,%: C 42.20; H 8.33; N 9.81; P, 10.9V. C-foH lOfP Calculated,%: C 42.25; H 8.86; N 9.85; P 10.90. PRI mme R 2. Choline OL-AMPB. 2.49 g of the barium salt of DL-AMPB is dissolved in 25 ml of water and 1.52 g of choline sulfate is added. The precipitate of the resulting barium sulfate is filtered off and the filtrate is condensed. The residue is dissolved in 25 ml. ethanol and white precipitate are recovered by adding 250 ml of acetone. The upper layer is discarded by decantation, the precipitate is washed with a small amount of acetone and dried under vacuum over phosphorus pentoxide to obtain 2.75 g of choline DL-AMPB in the form of a white powder, melting at 152-157 ° C. The results of elemental analysis,%: Found%: C 42.18; H 8.82; N 9.79; R 10.97. .05R Calculated,%: C 42.25; H 8.86; N 9.85; R 10.90. Froze Choline SF-1293. 3.23 g are dissolved in 25 ml of boiled and cooled water and 1.21 g of choline is added. The mixture is concentrated and the residue is dissolved in fe 25 ml of methanol. A white precipitate was isolated by adding 50 ml of diethyl ether. The upper layer is discarded by decantation and the precipitate is washed with a small amount of diethyl ether and dried in vacuum over phosphorus pentoxide to obtain 4.26 g of choline SF-1293 in the form of a white powder melting at 110 ° C. The results of elemental analysis,%: Found,%: C 45.02; H 8.23; N 13.10, P 7.33. C ,, 0-, P Calculated,%: C 45.07; H 8.27-, N 13.14; R 7.26. Compounds of general formula 1) nodify annual grasses with strong reproducibility, such as Digitaria adscendens Genr. and SchinochBoa Crur-gaEEi P.BOB. and inhibit their reproduction. If these herbicides are used to apply perennial weeds to the foliage, they are moved to subterranean parts, such as rhizome, tubers, bulbs, corms, and roots, which are the basis of perennial weeds, kill the subterranean parts. As a result of this, perennial weeds are destroyed by the introduction of a preparative preparation. Etc. to the foliage, which prevents the reproduction of nosome parts and which is the most difficult, but also the most important, in the fight against perennial weeds. There are only a small number of herbicides that effectively fight shrubs. If the proposed compounds are used for foliar treatment, they are transferred to any part of the plant and exhibit a strong deleterious effect and inhibitory effects: reproduction. The effects that inhibit the reproduction of cogs and shrubs, observed when using the proposed compounds, are superior to those observed when glyphosate is consumed. The proposed compounds are more effective than glyphosate at a lower concentration, since the latter has a weak effect when used to control broadleaf weeds and bushes, and the proposed compounds show very high activity in almost all weeds and shrubs, with the exception of the Japanese bale rice, and have an extremely wide range of effects in weed control. When comparing the activity in boron with weeds for L1-1PB choline and SF-1293 choline with the activity of AMPB mono-sodium salt or monodietano (AMPB ammonium salt and monosodium salt) (1-2-amino-4-hydroxy-phosphinoylbutyryl) - L-alanyl-L-alanine (hereinafter referred to as SF-1293) or monodiethylammonium salt of SF-1293, respectively, found that the proposed compounds are superior to herbicides that meet the previous level of technology in terms of the effect of destruction, ground parts and effects inhibiting reproduction. In particular such A distinction is made for effects that inhibit reproduction. L-AMPB choline, for example, is twice as effective as monosodium mono-diethylammonium salt L-AMPB (Test 1). One of the characteristics of the proposed compounds is that they are rapidly absorbed and penetrate into the plants after they are applied to the foliage | and are not exposed to rains. In addition, these compounds contain weeds and shrubs and inhibit reproduction and regeneration for a long period of time. The number of active ingredients are given in table 2. Preparation 1. Dust preparation. Choline L-AMPB 4.0%, 95.0% talc and 1.0% fine silicic acid powder are pulverized and mixed to form a dust preparation. For application to weeds and shrubs growing in mountainous areas and in lowlands, this preparation is applied to listia as such. Drug 2. Liquid drug. 30.0% SF-1293 choline, 15.0% octyl phenylpolyoxyethanol, 0.15% methyl p-hydroxybenzoate and 54.85% water are mixed to form a solution and get a liquid preparation. For application on weeds and shrubs growing on mountainous areas and on lowlands, this preparation is diluted with water and put on foliage. Preparation 3. A wetting powder, 45.0% DL-AMPB choline, 50.0% diatomaceous earth, and 5.0% non-ionic / anionic surfactant are powdered, mixed to obtain a homogeneous mixture, and a JCO grind is used to obtain wetting the naked powder. For application to weeds and bushes growing in mountainous areas and on lowlands, the preparation is diluted with water and applied to foliage. The drug 4. Liquid drug. Choline 30.0% DL-AMPB, 15.0% octylphenylpolyoxyethanol, 0.15% p-hydroxybenzoic acid methyl ester and 54.85% water are dissolved and mixed to form a liquid preparation. For application to water plants, the mixture is diluted with water and applied to the leaves or to the underwater parts. Preparation 5. Wettable powder. 50.0% L-AMPB choline, 45.0% diatomaceous earth, and 5.0% non-ionic / -anionic surfactant are pulverized and mixed to obtain a homogeneous mixture, which is subjected to final grinding to obtain a fine powder. For application to water plants, the powder is diluted with water and applied to the leaves or underwater parts of plants. Preparation 6. Dust preparation. 5% SF-1293 of choline and 95% talc-pre-g are rotated into a powder and mixed to obtain a homogeneous mixture to form a dust preparation. For application to water plants, it is applied to the leaves in the amount of 0.4-6 kg per 10 ares. To assess the results of the following experiments, use the following scale Indicator Damage of leaf destruction,% 0.O 120 240 3.60 4 to 5; 10-0 But after 4 months. after processing, a reproduction inhibition effect is evaluated, which is expressed in characters from (-) to (+++) where (-) means no reproduction, namely complete reproduction of reproduction "and, and (+) - strong reproduction reproduction, ( +) significant repression suppression, {++) mean reproduction suppression and (+++) lack of reproduction reproduction. , Test 1: Compounds of general formula (I) and other compounds used for comparison, listed in Table 3, are diluted to the prescribed concentration and sprayed. by nodding at weeds growing in natural weeds, by applying to the truth in the amount of 150 l per 10 ars. - b as a surfactant 0 substances added 10% octyl-phenyl-, polyoxy-ethanol.

The destruction indicator is determined where O is the absence of effect; 5 - death), after 21 days and the effect of inhibition of reproduction (-) - no reproduction, {+++} - maximum reproduction) after 2 months (Digitaria adscendens u Ech i n-och Roa-Crur-ga Ppe) and 4 months old weeds) .. The results are shown in Table. 3

OnjT 2. Compounds of general formula CI) and other compounds listed in Table 4 are diluted to the prescribed concentration and sprayed onto bushes by spraying the leaves with a Japanese cypress in the amount of 150 l per day. 10 ares.

After 30 days and 3 months, the destruction indicator is determined (O - no effect, 5 - death). Plant height is as follows: 50-70 cm for the Japanese cypress, about 50 cm for the chestnut, 50-90 cm for the long. Sasa nipponicaj about 100 cm for Miscanthus sinensis and 70-100 cm for Ru.buscratacgifoEins respectively. The results are shown in table 4.

Experiment 3. Compounds of general formula (1) and other compounds listed in Table 5 are diluted according to the prescribed concentration and applied to natural bushes growing by treating their foliage in the amount of 150 liters per 10 ars.

0.1% octylphenylpolyoxyethanol is added as a surfactant. The destruction rate was determined (O - no effect, 5 - death) after .1 months and 3 months and reproduction inhibition effect (-) - no work, (+++) - maximum reproduction) after 3 months.

The results are shown in table.5.

Experience 4. Water is placed in containers made of plastic material, size

20X 30 cm and liquid fertilizer is added to the water .. Two plants of E ichornia crassipes Solms are melted in each tank. To Oh, 1-0,2% aqueous solution of Dl. choline is added 0.1 or 0.2% of each of the surfactants listed in Table 6. Each solution was sprayed onto the foliage in an amount of 100 liters per 10 ars. Determine the rate of destruction (O - no effect, 5 - death) after

21 days and 3 months and the effect of inhibiting reproduction (-) - no reproduction, (+++) maximum reproduction after 3 months. The results are shown in Table. 6

Experience 5. In a container of plastic material, size 20 x 30 cm

water is added and liquid fertilizer is added. In a kaafy vessel, two Eichhornia crassipes So I ins plants are placed, which. float on water, 100 l per 10 aps of 0.1 or 0.2% solutions of each of the compounds listed in Table 7 are applied to the leaves of plants; 0.1% octylphenyl polyoxyethyl 0 is added as a surfactant nola. The destruction rate was determined (o - no effect, 5 death) after 21 days and 3 months | And the reproduction inhibition effect (-) - no reproduction, (+++) - maximum reproduction) after 3 months. The results are shown in table 7.

Experience b. The soil from the rice floor is placed in square ,, with a side of 50 cm,

Q pots of concrete. On this soil

Sagittaria trifolia L, Sagittaria pygmala Hig, Hydrocharis dubia and Sagittaria Aginashi Ma kino plants are transplanted, after which the soil is filled with water with a layer height of 5 cm.

EichHernia crassipes, spirode a poBy ghiza SchPeid and Lemna paucicostata Hegelman are allowed to float on the surface of the water.

After 1 month, compounds of general formula (Q) are applied in amount. 100 l per 10 ares, and the leaves are treated. The concentration of the compounds is chosen in accordance with the prescribed and given

5) in table.8. 0.1% octylphenylpolyoxyethanol is also used as a surfactant.

The destruction rate was determined (O - no effect, 5 - gib / after 21 days and 3 months and the effect of inhibition of reproduction ((-) no reproduction, (4 - ++ - maximum reproduction after 3 months.

5 The results are shown in TK table. eight.

Experience 7. The chernozem is placed in a square section of pots from

The concrete Q with a side of 50 cm and the soil is poured with water in a layer of 50 cm. Plants SagatophyEEum demersum L, Chara B g u u p i i 1 chalk. and Salvinia natans ABE are transplanted into pots, and on the surface of WATER they are allowed to float by Spirogira crassa Kutz and BaclEBariophyta. Thereafter, the compounds of the general formula (.1) are dripped onto the surface of the water so that the prescribed concentration in the water given in Table 9 is created in the water. The destruction rate is determined (O - no effect, 5 - excellent destruction) after 21 days and 3 months. The results obtained when

5 are listed in table 9. L-AMPB indicators Choline Appearance White powder Melting point, ° C Sintering at 135, melting at 175178

 R

C 42.20; H 8.83; N 9.81; Р 10.98 13.8 ° Specific rotation (, methanol) Absorption in the UV absorption by the condensate groups Mass spectrometry285 (M + I) and Solubility, 95 (Ethanol) mg / ml

Thin layer

0.31 chromatography

CioHjsN-zOsP

C, t,

C 42.18; H 8.82; C 45.02; H 8.23, N 9.79; Р 10.97 N 13.10, Р 7.33

0.31

0.31. Table 1 DL-AMPB choline 1 SF-1293 choline Belki powder White powder Sintering under Plavits at 105, melted 110-112 at 152-157 0.0 °, CcLJ - 1.2 (, methanol) (, methanol) Absorption; Absorption by end groups by end groups 285 (M + 1) iet (Ethanol) 310 (Ethanol)

Note: AMPB choline - 2 amino-4 (oxy) (methylHphosphinoylbuty-. Rilcholine, SF-1293 choline - C2-amino-4- (oxy.) (Methyl | fofefinoylbutyryj-anapanyl Eshaninholina.

in1Л

in1Л

ITLITI

m1Л

ui

1Л1Л

1Л1Л

1Я1Л

1Л1Л

el1l

1Л1Л

I

u s

Q. A

H c;

(and about CQ X and Dj

0s

1 to

h 1c I

about sh -

in

tHin

“Chin

Hin

4in

hchin

HCN

roin

min

fn401in

nin

ro in

mn

Monostearate

POLYOXYETHYL L-Sorbitam

Polyoxyethylene sorbitan monooleate

Octylphenylpolyoxyethanol

Polyoxyethylene Ashkilaryl Ether

Simple dodecyl ether. Polyoxyethylene

No surfactant

Table b

4.5

2 ++

S 5

4 ± 5

4.5

24-45 5

5 4+

five.

3+

5 5

five

4.5+

five

4.5

2 ++

5 5

4 ±

five

4.5

2 ++ 5

4+

4.5 ±

1 +++

Continued table. 7

35 97571236

Claims (3)

The formula of the invention is a general formula Phosphorus-containing derivatives  Q CHj-P-CCHjl-ji-CH -АP-СОО (СНэ) е1-СН2СН20Н . V. -Oh. PH of pH 1. USSR Patent 580841, yes .. „0-MH-CH cl. C 07 F 9/38, 1975. . . -. 2. Japan Patent No. 52-158932, , n: i O or 1,10 kl. 16C 412, published. 1977. having herbicidal activity. Information sources, 3. Japan patent No. 5.3-036059, taken into account during examination. 16 C 412, published. 1978