SU991952A3 - Process for preparing choline derivatives - 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

to / or 2-amino-4 (oxy) (methyl) -phosphine ilbutyrylcholine of Formula 2: O CHjPiCHj j-CH-COO (CH,) KCHjCH20H, according to which choline and / or inorganic salt of holim is reacted. with 2-amino-4 (oxy) (methyl b phosphinoyl butyryl T-alanylalanine and / or 2-amino-4- (oxy) (methyl b-phosphine ilbutanoic acid and / or its -sol.  Compounds of formula 1 or 2 can be prepared by adding equimolar amounts of choline or its inorganic salt, for example choline sulfate, to an aqueous solution of a compound of formula 3 in which M is a hydrogen atom, or by adding an equimolar amount of choline salt with sulfuric acid to an aqueous solution of a compound of formula 3 in which M is a metal, for example barium.  It is preferred to use carbon dioxide-free water, since choline tends to form carbonate.  This aqueous solution is concentrated to dryness, the residue is dissolved in a 10-fold volume of solvent, such as methanol or ethanol.  The desired compounds are isolated by adding 40 to 50 times the volume of an organic solvent, such as ethyl acetate, chloroform, benzene, or diethyl ether.  Get white oh. A tank that is dried under vacuum in the presence of a drying agent produces the choline compound of formula 1 or 2 as a white powder.  If an inorganic salt is formed as a by-product, then compounds I or 2 can be separated from the concentrated reaction solution using alcohol or its mixture with acetone (when the inorganic salt is soluble in water).  If the inorganic salt is poorly soluble in water, such as barium sulfate, it can be removed from the reaction solution by filtration or decantation.  Example 1  Choline L-AMPB.  3.55 g of L-AMPB is dissolved in 50 ml of boiled and cooled water and 2.38 g of choline is added to the mixture.  The mixture is concentrated and the resulting residue is dissolved in 50 ml of ethanol.  A white precipitate was isolated by adding 500 ml of ethyl acetate.  The upper layer is decanted, the precipitate is washed with a small amount of ethylacetate and dried in vacuum over phosphorus pentoxide.  Obtain 5.4 g of choline L-AMPB in the form of a white powder, t. square  175-178 C.  Found,%: C 42.20; H 8.83; N9.81; P10.98.  .  C, o 1125 RUR calculated,%: C 42.25; H 8.86; N 9.85; R 10.9.  Example 2  Choline DL-AMPB.  2.49 g of the barium salt of OL-AMPB is dissolved in 25 ml of water and 1.52 g of choline sulfate is added.  The precipitate of barium sulphate formed is filtered and the filtrate is condensed.  The residue was dissolved in 25 MP of ethanol and the white precipitate was made by adding 250 MP of acetone.  The upper layer is decanted, the precipitate is washed with a small amount of acetone and dried in vacuum over phosphorus pentoxide.  2.75 g of choline OL-AMPB is obtained in the form of a white powder.  T. square  152-157C.  Found,%: C 42.18; H 8.82; N 9.79; R 10.97.   W iOfpc 42.25; And 8.86; Calculated,%: N 9.85; R.  10.90.  3  Choline SF-1293.  . Example 3.23 g of SF-1293 was dissolved in 25 ml of boiled and cooled water and 1.21 g of choline was added.  The mixture is concentrated and the residue is dissolved in 25 ml of methanol.  A white precipitate was isolated by the addition of 50 MP diethyl ether.  The upper layer is decanted, the precipitate is washed with a small amount of diethyl ether and dried in vacuum over phosphorus pentoxide.  4.26 g of choline SF-1293 are obtained in the form of a white powder.  .  T.  square  .  Found,%: C 45.02; H 8.23; N 13.10; R 7.33.   Ns5 N4 & P.  Calculated,%: C 45.07 / H 8.27; N 13.14; R 7.26.  Physical constants and physicochemical characteristics of the compounds obtained are given in table.  one.  The growth of perennial weeds is a problem not only in areas not suitable for growing crops, but also in the fields for rice, in mountainous areas, orchards and meadows.  . The complete destruction of perennial weeds can only be achieved with reproduction inhibition.  However, perennial weeds are more resistant to herbicides than annual ones.  To date, i used N-phosphonomethylglycine (glyphosate) to control many summer weeds, but this substance is not effective for killing broadleaf weeds.  Therefore, it is desirable to obtain herbicides with a wider spectrum of weed control.  The proposed new compounds kill annual grasses with strong reproducibility, such as Oigltaria adscendes Genr.  and Echlnochloa Crus-galli P. BOB. and inhibit their reproduction.  If these herbicides are applied to the foliage of perennial weeds, they are moved to subterranean parts, such as rhizome, tubers, and bulbs,.  corms, roots and kill under terrestrial parts.  In this case, multiple weeds are destroyed by preventing the reproduction of underground parts, which is most important in controlling them.  There is also a serious problem of the destruction of shrubs in the fields that are no longer suitable for cultivation of cultivated plants, in meadows and in areas planted with forest.  Only a small number of herbicides are effective in the fight against shrubs.  Compounds of formulas 1 and 2 exhibit a strong destructive effect and effects, inhibiting reproduction, when treating foliage of bushes, as they move to any part of the plant.  From practice, it is known that a small number of herbicides are effective at the same time for the destruction of weeds and shrubs.  For example, the sodium salt of 2,2,3,3-tetrafluoropropionic acid is an effective herbicide for killing the herb Mi cantus sinensis and bamboo in forest areas, but it is not the same. effective for shrubs, and shrubs such as Rubus crataeg1fopus, chestnut trees (Castanea crenota) and danska cranberries begin to grow after killing Miscantus sinensis grass and bamboo, which requires the additional use of herbicide to combat the growth of shrubs.  In contrast, compounds of the formula 1 or 2 can simultaneously destroy billers and shrubs and inhibit their reproduction and regeneration for a long period of time.  The proposed compounds are fast.  are absorbed and penetrate the plants after applying them to the foliage, t. e.  possess resistance to rain.  This feature makes them preferable in those conditions when plant metabolism is low and the absorption and penetration of herbicides is inhibited or when the compounds are sprayed at a low temperature or at a later stage of plant growth during autumn processing.  In addition, the proposed compounds are suitable for the treatment of areas planted with forest, as they give a high effect in the fight against large perennial weeds and shrubs.  Since they do not possess phytotox ACCURACY in relation to JAPAN cypress, they can be used as selective herbicides in areas planted with Japanese cypress to combat ground-based weeds.  The proposed compounds can also be used to control weeds in their ground time ± and for a long time, if they are applied before sowing, without any phytotoxicity for evicted plants.  When used in rice fields during autumn processing (after harvesting; to destroy perennial weeds), they move through the plants and inhibit the reproduction of their underground parts during the subsequent spring.  Since they deactivate relatively quickly in the soil, adsorbing on its surface, they can also be consumed in fruit areas, while they do not create phytotoxicity for plants, since they are not absorbed from plant roots.  The proposed compounds may thus be used in various regions, except for the areas planted with forest and the areas on which the cultivated plants are grown.  For example, in the meadows where livestock grazes, bushes often grow. Their competitor on pastures is Rumex obtusifolius i. It is known that the quality of milk decreases in cattle that eat these plants.  Prickly weeds, such as Solanum carolinense L, can cause damage to cattle.  Compounds of formula 1 or 2 can destroy weeds and shrubs on pastures if applied in a dotted manner.  In addition, these compounds can be used to control annual and perennial weeds and bushes in factories, railways, parks, public places, on the slopes, shallows, highways, golf courses, located under the steam. areas for growing cultivated plants and virgin zeglles.  The number of compounds required to kill weeds and shrubs and to inhibit reproduction can vary depending on climatic conditions (temperature and light intensity), as well as the types of weeds and shrubs to be destroyed.  The number of active ingredients is shown in table.  2  Compound. Formulas 1 and 2 can effectively destroy not only plants growing in mountainous areas and lowlands, but also algae, and higher aquatic plants (plants taxonomic more developed than algae), for example, plants that are completely in the water and their roots extend below the lower water level, those plants, some of which are.  protrudes from the water, and those that float on the water or in the water column.  Aquatic plants create various inconveniences, for example, if weeds bloom on the waterway, the flow rate of water in rivers decreases as compared to the original planning.  This causes sedimentation. soil and sand, changes in water temperature, increased erosion of the water channel, interruptions in the passage of transports along the river path and a decrease in the number of fish.  Besides, . there are serious problems in terms of water supply and drainage in canals, lakes and.  swamps and dam irrigation.  The growth of aquatic plants can make it impossible to swim and fish in lakes and swamps, greatly reduce the possibility of using water for industrial purposes and degrade the appearance of landscapes during sightseeing, the anti-biological activity of these compounds is caused by their penetration and absorption on the surface of plants and moving inside plants after penetration.  In the case of perennial weeds such as Eichhormocrassipes Solms, the compounds completely inhibit the reproduction of new leaves, resulting in the death of the plant.  In addition, these compounds destroy algae, such as Splrogyra and Diatomacae.  The greatest advantage of the compounds of formulas 1 and 2 when using them to control aquatic plants is that they have very low toxicity to fish (LC5o20 hours).  by 10,) and excellent selectivity for fish, plants and algae, which should be controlled if the compounds are applied to leaves of aquatic plants that float on the surface of the water or grow on the surface of the water and extend their roots below the bottom water levels, they are diluted with water and do not create any toxicity to fish at all.  When using the proposed compounds to obtain floating preparations, they form a thin layer on the surface of the water for a certain period of time and are rapidly absorbed by weeds growing near the surface of the water, and at the same time they are not dangerous for fish.  Thus, enhancing the effect and preventing toxicity for fish is achieved at the same time, which makes it possible to consider the proposed compounds as valuable herbicides for aquatic plants.  The amount of compounds that is needed to destroy aquatic plants varies depending on various conditions.  If the compounds are applied to the leaves, water plants and algae can be destroyed by spraying with a solution containing 0.01-1.0% of the active ingredient in 25-250 p. Of water per 10 are. If compounds are introduced below the water level, water plants and algae can be destroyed, while maintaining the concentration of the active ingredient in the quiescent water 0.1 to 20 hours per 10.  The proposed compounds in some cases absorb moisture during prolonged storage, however, they can be considered as resistant herbicides.  To combat weeds and shrubs growing in mountainous areas and in lowlands, as well as with water plants and algae, the proposed compounds can be used in the form of liquid and water-soluble preparations, wettable powders, emulsifiable concentrates, preparations in the form of dust, fine granules, etc. d.  These preparations may contain surfactants such as octylphenylpolyoxyethanol, polyoxyethylene dodecyl ether, ester formed from polyoxyethylene sorbitan with fatty acids, alkaryl ether, polyoxyethylene ether, or the like. P. which serve to improve.  the ability to spread, the properties of adhesion or dispersion and provide the necessary effects or even enhance them.  In addition, the preparations may contain other herbicides, for example, inhibitory germination and agents that promote their application to the foliage, to enhance the effect of the proposed compounds and to prolong the period of their effective action.  Various formulas of drugs obtained as follows.  Drug 1.  Dust preparation.  4.0% L-. AMPB of choline, 95.0% talc and 1.0% fine powder of aqueous silicic acid is converted into nopotiOK and mixed to form a drink preparation.  For application to weeds and shrubs growing in mountainous areas and in lowlands, this preparation is applied to the foliage in the form of dust.  Preparation 2.  Liquid preparation.  30.0% SF-1293 chloma, 15.0% octylphenylpolyoxyethanol, 0.15% methyl para-oxybenzoate and 54.85% water are mixed to form a solution and a liquid preparation is obtained.  In order to affect the weeds and bushes growing in mountainous areas and lowlands, this preparation is diluted with water and applied to the foliage.  Preparation 3.  Wettable powder.  45.0% choline DL-AMPB, 50.0% diatomaceous earth, and 5.0% non-ionic / anionic surfactant are pulverized, mixed to obtain a homogeneous smosi and finely and are chalked out .  To affect weeds and bushes growing in mountainous and lowland areas, the preparation is diluted with water and applied to foliage.  Formulation 4.  Liquid preparation.  30.0% OL-AMPB hopin, 15.0% octyl phenylpolyoxyethane, 0.15% p-hydroxybenoic acid methyl ester and 54.85% water are dissolved and mixed to form a liquid preparation.  To affect water plants, the mixture is diluted with water and applied to the leaves or to the underwater parts.  Preparation 5.  Weeping with a 50.0% L-AMPB choline powder, 45.0 diatomaceous earth, and. the non-ionic / anionic surfactant is powdered and ' mixed to obtain a homogeneous mixture, which is finally ground by grinding to obtain a fine powder.  To affect the water plants, the powder is diluted with water and applied to the leaves or underwater parts of the plants.  Formulation 6.  Dust preparation.  Choline 5% SF-1293 and 95% talc are pulverized and mixed to obtain a homogeneous mixture to form the PELLI preparation.  To affect water plants, it is applied to the leaves in an amount of 0.4-6 kg per 10 ares.  To evaluate the results, the compounds of the formula l or 2 were used; the following was applied: Scale: Destructive damage to leaves,% Evaluation of the effect and inhibition of reproduction expressed in.  interval from (-) to (+++), where {-) denotes the absence of reproduction, namely complete repression suppression (t) - strong reproduction suppression, (+) - significant reproduction suppression, (++) - mean reproduction suppression and (+++) - the absence of reproduction reproduction.  .  EXAMPLE 1.   The proposed and known compounds used for comparison are diluted to the prescribed concentration and sprayed under natural conditions, weeds applied to the leaves in an amount of 150 liters per 10 ares.  10% octylphenylpolyoxyethanol is added as surface active.  The destruction rate after 21 days and the effect of inhibiting reproduction after 2 months (Oigitaria adscendes and Echtnochloa Cg5-daP |) and 4 months (other weeds) are determined.  The results are shown in Table.  3   Experience .  2  Predicted and known compounds are diluted to the prescribed concentration and sprayed onto the shrubs by treating their foliage / on a plot planted with Japanese cypress, in an amount of 150 liters per 10 ares.  After 30 days and 3 months, a kill rate is determined.  Plant height is as follows: 5070 cm for Japanese cypress, about 50 cm for chestnut, 50-90 cm for Sasa nipponica, about 100 cm for Miscanthus sinensis and 70-100 cm for Rubus erataegifo1ius, respectively.  The results are shown in Table B.  four.  Experiment. .  The proposed and known compounds are diluted to the prescribed concentration and applied to shrubs in natural conditions by treating their foliage in an amount of 150 liters per 10 ares.  0.1% octylphenylpolyoxyethanol is added as a surfactant.  The kill rate after 1 and 3 months and the effect of replay inn were determined.  after 3 months  The results are shown in Table.  five.  About 4.  Water is placed in an e-lacquer of plastic material of size 20 x 30 cm and liquid fertilizer is added to it.  Two Eichho plants, Solms crassipes, are allowed to float in each tank.  To a 0.1-0.2% aqueous solution of DI-AMPB choline was added 0.1 or 0.2% of each of the surfactants listed. in tab.  b.  Each solution is applied by spraying the leaves in an amount of 100 liters per 10 ares.  The destruction rate is determined after 21 days and 3 months and the effect of reproduction inhibition after 3 months.  The results are shown in Table.  b.  Experience 5.  In containers of plastic material with a size of 20 x 30 cm, water is poured and liquid fertilizer is added.  Each plant is placed in two plants that float on the water.  On the leaves.  plants are applied in an amount of 100 liters per 10 ares 0.1 or 0.2% solutions of each of the proposed and known

compounds. 0.1% octylphenylpolyoxyethanol is added as a surfactant. The destruction rate is determined after 21 days and 3 months and the effect of inhibiting reproduction after 3 months. The results are shown in Table. 7

About bs

The soil of the rice floor is placed in square, with a side of 50 cm, pots of concrete. H, and Sag 11taria tr folia L, Sagittaria pygmaea Mlg, Hydrocharls dubla and Sagittaria Aginashi Makino plants transplant this soil, and then pour 5 cm of water over the soil on the soil. Next, Eichhornia crassipes, Spirodela polyrhea Schleld and Lemna pauclcostata Hegelma. After 1 month, the proposed compounds are applied in an amount of 100 liters per 10 ares, and the leaves are treated, and the concentrations of the compounds are collected in accordance with the prescribed and table. 8. As a surfactant, 0.1% octylphenylpolyoxyethanol is used. The destruction rate is determined after 21 days and 3 months and the effect of inhibiting reproduction after 3 months. The results are shown in Table. 8. - About p. 7

The black earth is placed in square pots of concrete with a side of 50 cm and 50 cm of water is poured on the soil. Ceratopyl 1um demersum L, Chara Braunif and Salvina natans All asthenia are transplanted into pots, and on the surface of the water they are allowed to float Ira crassa Kumya and you And 1 and giophyta. After

To this end, offer compounds that are applied dropwise to the surface of the water so that their concentration is necessary in the water. Determine the rate of destruction on the solution 21 days and 3 months. The results are shown in the table. 9.

Given in Table. . Figures 3–9 show that the effects inhibiting the reproduction of weeds and shrubs observed with the use of the proposed compounds are superior to those observed with glyphosate intake. In addition, the proposed compounds are more effective than glyphosate at a lower concentration.

While glyphosate has a weak effect when it is used {13 to control broadleaf weeds and shrubs, the proposed compounds show very high activity for almost all weeds and shrubs, with the exception of Japanese cypress, and have an extremely wide range of effects when with weeds.

From a comparison of the activity in the control of weed for AMPV choline and SF-1293 choline with the activity of the monosodium salt of AMPV or the monodiethanolammonium salt of AMPV and the monosodium salt (L-2amino-4- (oxy) (methyl) phosphinoyl butyryl) -alanyl-1- alanine (SF-1293) or monodiethylammonium salt has been established that the proposed compounds are superior to known herbicides in terms of both the effect of killing terrestrial parts and the effects inhibiting reproduction. L-AMPB choline, for example, is twice as effective as monosodium or monodiethylammonium salt L-AMPB (Table 3.)

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Table 6

+++

Table 7

OL-AMPB Monosodium Salt

Continued table. 7

4-4.

DL-AMPB two-potassium salt

DL monodiethylammonium salt

DL-AMPV mono-propylammonium salt

DL-AMPB mono-n-butylammonium salt

OL-AMPV diammonium salt

DL-AMPB

Continued tabl, 7

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Claims (3)

± ++ 41 Claim for the preparation of choline-2-amino-4- (oxy) (methyl) -phosphinoylbutyryl-alanylalanine choline derivatives of the formula I: §S. , - J1 | П CHj CHjp-lCHiijCHcoKHCHCONH-CHcooicHj JicH ,, CH o l ".ii o MHj and / or 2-amino-4- (oxy) (methyl) -phosphonylbutyrylcholine of the formula 2: .1 t, CHjP- ( CHj) 2-CHCOOJlCH,) jNCH eH20H l- + L. NH. 3 characterized in that choline and / or inorganic choline salt 195242 is reacted with and -amino 4 (oxy) {methyl) -phosphonic1. Butyrnyl-alanylalanine and / or 2-amino-4- (oxy) {ethyl; - (1-syphinoylbutano acid and / or its salt, Sources of information taken into account during the examination 1. Japanese Patent No. 48-22688, Q C. 16 C 412 published 1973. 2. Japanese patent 49-31890, cl. 16 with 412, published. 1974. 3. Japanese patent 48-85538, cl. 16 C 412, published. 1973. .. 4, Japanese Patent 52-158932, 15 kl. 16 C 412, published. 1977. 5. Japanese Patent No. 53-036059, cl. 16 C 412, published. 1978