EP0000767B1 - Dérivés de l'acide glycylméthyl-phosphinique, leur préparation et leur utilisation - Google Patents

Dérivés de l'acide glycylméthyl-phosphinique, leur préparation et leur utilisation Download PDF

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Publication number
EP0000767B1
EP0000767B1 EP78100567A EP78100567A EP0000767B1 EP 0000767 B1 EP0000767 B1 EP 0000767B1 EP 78100567 A EP78100567 A EP 78100567A EP 78100567 A EP78100567 A EP 78100567A EP 0000767 B1 EP0000767 B1 EP 0000767B1
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Prior art keywords
formula
acid
radical
group
benzyl
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EP0000767A1 (fr
Inventor
Ludwig Dr. Maier
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Novartis AG
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Ciba Geigy AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C07F9/301—Acyclic saturated acids which can have further substituents on alkyl
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C07F9/32—Esters thereof
    • C07F9/3205—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/3211—Esters of acyclic saturated acids which can have further substituents on alkyl

Definitions

  • the present invention relates to new glycylmethylphosphinic acid derivatives, processes for producing the same and the use of the new derivatives as active ingredients in herbicidal and plant growth-regulating agents.
  • R is preferably hydrogen or an easily removable radical (benzyl, tert-butyl, di- or triphenylmethyl).
  • R ' is the ⁇ OH group and / or R "is hydrogen, ie the compounds of the formula I have at least one free acid group
  • acids are capable of forming salts with bases, both by means of the carboxylic acid group and by means of the phosphinic acid group
  • Suitable salts are the ammonium and metal salts of the alkali and alkaline earth metals (Li, Na, K, Ca, Mg), but also of other metals such as Fe, and salts of amines, such as alkyl and alkyl amines, or of quaternary ammoniobases ; Examples of amines are: methylamine, isopropylamine, tert-butylamine, allylamine.
  • R 1 is a lower alkenyl, alkynyl or alkyl group
  • the end products are esters.
  • R " is lower alkyl, but preferably hydrogen or a cation of the type described for R '.
  • Example of a hydroxyalkyl radical R" is ⁇ -hydroxyethyl.
  • R "' is preferably a C 1 -C 4 alkyl radical, in particular methyl or ethyl.
  • substituted alkyl radicals hydroxymethyl, trichloromethyl, dichloromethyl, trifluoromethyl, ⁇ -chloroethyl etc. may be mentioned.
  • R"' is substituted, the substituents are primarily halogen atoms, lower alkyl and haloalkyl groups and dialkylamino groups are considered.
  • hypophosphorous acid with formaldehyde and piperidine (unsubstituted secondary amine) in strongly hydrochloric acid solution gives the hydrochloride of bis (piperidinomethyl) phosphinic acid [Helv. Chim. Acta 50, 1742 (1967)].
  • the process according to the invention for the preparation of the new glycylmethylphosphinic acid derivatives of the formula I is characterized in that an N-substituted glycine of the formal 11.
  • R 2 is a C 1 ⁇ C 6 alkyl radical, preferably a removable alkyl radical such as tert-butyl, the benzyl, di- or triphenylmethyl radical or the group -CH 2 COOH, with formaldehyde and a phosphonous acid of the formula III wherein R '"is defined under formula, is reacted in an acidic aqueous medium and the glycylmethylphosphinic acid derivative of the formula Ia obtained if desired by splitting off a cleavable group R 2 and / or further post-operations into a salt. transferred another derivative of formula I.
  • R 2 is preferably a cleavable radical, such as tert-butyl, benzyl, di- or tri-phenylmethyl, or another acetic acid group -CH 2 COOH.
  • a corresponding dihalophosphine in particular dichlorophosphine of the formula R "'- PCl 2 , can be used, which is immediately hydrolyzed to the phosphonous acid derivative of the formula III in the aqueous acidic reaction medium.
  • the reaction is advantageously carried out in a strongly hydrochloric acid environment (pH ⁇ 5), at temperatures of 20-100 ° C and takes about 2 to 4 hours.
  • a strongly hydrochloric acid environment pH ⁇ 5
  • it is advantageous to work in the absence of oxygen. Good yields are obtained especially when an excess of formaldehyde is used.
  • R '"in the starting material III and in the end product la is an alkyl radical, the latter is obtained in the form of the hydrochloride.
  • R"' is an electronegative substituent, such as hydroxymethyl, trichloromethyl, chloroethyl or phenyl, the end products of the formula la crystallize without HCl, ie the phosphinic acid proton is so acidic that the acids obtained form an inner betaine.
  • the group R 2 can be cleaved off after the reaction to give the phosphinic acid derivative la.
  • Suitable R 2 radicals which can be removed are tertiary C 4 -C 6 alkyl radicals, in particular tert-butyl or aromatically substituted methyl groups such as in particular benzyl, and also diphenylmethyl and triphenylmethyl.
  • a phenylated methyl radical, in particular benzyl, is best eliminated by catalytic hydrogenation (catalytic debenzylation) with hydrogen in a solvent such as water, glacial acetic acid, aqueous acetic acid or a water / ethanol mixture.
  • a suitable catalyst is palladium (5%) on carbon; but you can also use platinum oxide or platinum / coal.
  • the hydrogenation is preferably carried out at normal pressure and temperatures between 20 and 50 ° C and takes between 10 minutes and 20 hours depending on the radical R 2 which is split off.
  • a further possibility of cleaving off these cleavable radicals R 2 is that an acid of the formula Ia or a salt thereof (for example the hydrochloride) at 100-200 ° with HBr in water or Glacial acetic acid, optionally under pressure, treated for one to 10 hours.
  • the conversion of acids of the formal I into corresponding salts, esters or amides is carried out using techniques known for such reactions, such as neutralization, treatment of alcoholic suspensions with HCl, etc.
  • N-substituted glycines of the formula II used as starting materials and the phosphonous acids of the formula III or the dichlorophosphines of the formula R "'- PCl 2 resulting from hydrolysis are known [" Organic Phosphorus Compounds ", ed. GM Kosolapoff and L Maier, John Wiley & Sons, New York 1972, Vol. 4, Chapters 8 and 10J.
  • the acid can be titrated with tetramethylammonium hydroxide as a three-base acid.
  • Example 1 According to the procedure described in Example 1, from 29.0 g (0.2 mol) of n-propyldichlorophosphine, C 3 H 7 PCl 2 , 60 ml of water; 40.3 g C 6 H 5 CH 2 ⁇ NH-CH 2 CO 2 H, 34.3 g 35% CH 2 O solution and 60 ml conc. Hydrochloric acid, after evaporation on a Rotävap 53.3 g (N-benzylglycylmethyl) propylphosphinic acid of the formula as a white crystalline substance, which melts after decomposing from water at 155-157 ° C with decomposition.
  • This compound can be titrated as a dibasic acid with 2 potential jumps (first jump at pH 6.3; second jump at pH 10.2).
  • Compound 7 can be titrated with (CH 3 ) 4 NOH in water with 2 potential jumps.
  • the monoethyl ester (esterified on the carboxylic acid group) of this dibasic acid is obtained by esterification with ethanol and hydrochloric acid.
  • the product obtained is the hydrochloride of the ester, of the formula and melts at 90-95 0 with decomposition.
  • Compound 10 can be titrated as a dibasic acid with 2 potential jumps.
  • the mono-isopropylamine salt of this compound is prepared by evaporating an aqueous solution of equivalent amounts of the above phosphinic acid and isopropylamine.
  • This acid can also be titrated with (CH 3 ) 4 N-OH as a dibasic acid with 2 potential jumps.
  • the mono-isopropylamine salt of this acid prepared by evaporating an aqueous solution of equivalent amounts of the acid and isopropylamine, melts at 194-197 ° with decomposition (yield 97%).
  • the new derivatives of formula I both those in which R is hydrogen and those in which R is a substituent (benzyl, etc.), have herbicidal and plant growth-regulating properties.
  • Both the free glycylmethylphosphinic acids and in particular alkali metal and amine salts and their esters can be used in particular as contact herbicides and growth inhibitors in post-emergent application.
  • the alkali and alkaline earth metal salts, iron salts etc., the salts of organic amines, protonated and quaternary nitrogenous basin are to be mentioned as active substances, in principle all cations which are physiologically compatible, including those which themselves have growth-inhibiting properties.
  • the invention also relates to herbicidal and plant growth regulating compositions which comprise a new derivative of the formula I as an active ingredient, and to processes for total and selective weed control in crop plants and for inhibiting the growth of monocotyledonous and dicotyledonous plants, in particular for inhibiting the growth of grasses, cereals, Soy and ornamental plants.
  • the agents according to the invention can be present in the customary formulations, as dusts, scattering agents, granules, as dispersible concentrates, such as wettable powders, emulsions, emulsion concentrates and pastes, and as solutions, in particular in water.
  • formulations are prepared using conventional carriers and additives using known techniques.
  • the preferred herbicide application of the new active ingredients and agents is post-emergent use as a contact herbicide.
  • Some active ingredients are translocated in the plant and are therefore particularly suitable for controlling perennial weeds.
  • Another interesting application for the inhibition of plant growth is a control of natural plant development, which slows down these processes. Artificially retarding phases can be created in plant development (side shoot formation, flowering, fruit set etc.). The process of regulating growth is applied at a specific point in time in the development of the plant.
  • the new acids and derivatives of the formula and their salts can be applied either before or after the emergence of the plants either to the seeds or to the seedlings, roots, stems, leaves, flowers or other parts of the plants. This can e.g. by applying the active ingredient itself or in the form of an agent. on the emerged plant and / or by treating the nutrient medium of the plant (soil).
  • the effect achieved primarily by the new active ingredients consists in the desirable reduction in the size of the plants, in particular the height. In general, this involves a certain change in the shape of the plant. In direct connection with the reduction in growth height, however, the plant is strengthened. Leaves and stems are stronger. The kink resistance is increased by shortening the internode spacing on monocotyledonous plants. In this way, crop failures due to thunderstorms, continuous rain, etc., which normally lead to grain storage, can be largely prevented. As a side effect, the reduced height of crops leads to a significant saving in fertilizers. This also applies to ornamental turf, sports turf or other green plantings.
  • the active ingredients to be used according to the invention thus intervene in the physiological process of plant growth and therefore represent growth regulators which act in the sense of a growth retardation.
  • the various inhibitory effects depend essentially on the time of application, based on the stage of development of the plants, and on the concentrations used. Growth inhibitors can also have the effect that the nutrients benefit the bloom and fruit formation to a greater extent, while restricting vegetative growth.
  • the active ingredients are usually used as formulated, i.e. after the addition of carriers and other substances.
  • methylphosphinic acid has a very pronounced herbicidal effect on Setaria, Lolium, Solanum, Sinapis Stellaria etc.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Molecular Biology (AREA)
  • Dentistry (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Plant Pathology (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (12)

1. Nouveaux dérivés de l'acide glycylméthylphosphinique répondant à la formule I
Figure imgb0044
et leurs sels, dans lesquels
représente l'hydrogène, un reste alkyle en C1―C6, benzyle, diphénylméthyle ou triphénylméthyle ou le groupe HOOC―CH2―,
R' représente un groupe -OH ou ―OR1, dans lequel R1 est un cation, un reste alkyle en C1―C6, un reste alcényle en C2―C3, lesreste propargyle ou le groupe amino,
R" représente l'hydrogène, un cation ou encore un groupe alkyle inférieur ou hydroxyalkyle, et
R"' représente un reste alkyle en C1―C4 qui peut être mono- ou poly-substitué par des halogènes, des groupes hydroxy ou carboxy, ou un reste phényle éventuellement substitué.
2. Dérivés de l'acide glycylméthyl-phosphinique selon la revendication 1 pour lesquels, dans la formule I, R représente l'hydrogène et R"' un groupe méthyle, trichlorométhyle ou hydroxyméthyle.
3. Procédé de préparation des dérivés de l'acide glyxylméthyl-phosphinique de formule 1 selon la revendication 1, caractérisé n ce que l'on fait réagir une glycine substituée à l'azote répondant à la formule II
Figure imgb0045
dans laquelle R2 représente un reste alkyle en C1―C6, de préférence un reste alkyle éliminable tel que tert.- butyle, ou un reste benzyle, di- ou tri-phényl-méthyle, ou le groupe ―CH2COOH, avec le formaldéhyde et un acide phosphoneux répondant à la formule III
Figure imgb0046
dans laquelle R"' a les significations indiquées en référence à la formule I, en milieu aqueux acide, après quoi, si on le désire, on convertir le dérivé d'acide glycylméthyl-phosphinique obtenu, répondant à la formule la
Figure imgb0047
par séparation d'un groupe éliminable R2 et/ou par d'autres opérations subséquentes, en un sel ou en 'un autre dérivé de formule I.
4. Procédé selon la revendication 3, caractérisé en ce qu'on utilise une glycine de départ de formule Il dans laquelle le reste R2 est un reste éliminable pris dans le groupe formé par les restes benzyle, di- ou tri-phénylméthyle ou tert.- butyle.
5. Procédé selon la revendication 3, caractérisé en ce que la réaction est effectuée en milieu fortement chlorhydrique à un pH inférieur à 5 et à des températures de 20 à 100°C avec un excès de formaldéhyde et de préférence à l'abri de l'oxygène.
6. Procédé selon l'une des revendications 3 à 5, caractérisé en ce que l'acide phosphoneux de formule III est formé dans le mélange de réaction par introduction d'une dihalogénophosphine de formule R"' -P(Hal)2, en particulier d'une dichlorophosphine, dans le mélange de réaction aqueux, l'hydrolyse provoquant in situ la formation du composé de départ de formule III.
7. Procédé selon les revendications 3 et 4, caractérisé en ce que, pour séparer un reste benzyle, diphénylméthyle ou triphénylméthyle R2 éliminable, on soumet le produit intermédiaire de formule la à hydrogénation catalytique.
8. Procédé selon la revendication 7, caractérisé en ce que le symbole R2 de la formule la représente le groupe benzyle et en ce que la débenzylation catalytique est effectuée à des températures de 20 à 50°C à l'aide d'un catalyseur d'hydrogénation consistant en palladium sur charbon.
9. Procédé selon les revendications 3 et 4, caractérisé en ce que, pour séparer un reste éliminable R2 pris dans le groupe formé par les restes tert.-butyle, benzyle, di- ou tri-phénylméthyle, on traite le produit intermédiaire de formule la par l'acide bromhydrique dans un solvent à des températures de 100 à 200°C.
10. Produit herbicide et régulateur de la croissance des végétaux, caractérisé en ce qu'il contient en tant que substance active un dérivé de l'acide glycylméthyl-phosphinique de formule I selon la revendication I ou un sel d'un tel dérivé.
11. Utilisation des substances actives de formule I et des produits en contenant en tant qu'herbicides de contact pour la lutte sélective contre les mauvaises herbes après sortie de terre.
12. Utilisation des substances actives de formule I et des produits en contenant pour l'inhibition de la croissance des végétaux mono- et dicotylédones.
EP78100567A 1977-08-11 1978-08-02 Dérivés de l'acide glycylméthyl-phosphinique, leur préparation et leur utilisation Expired EP0000767B1 (fr)

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CH988377 1977-08-11
CH9883/77 1977-08-11

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EP0000767B1 true EP0000767B1 (fr) 1980-11-26

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US (1) US4233056A (fr)
EP (1) EP0000767B1 (fr)
JP (1) JPS5430117A (fr)
CA (1) CA1118784A (fr)
DE (1) DE2860342D1 (fr)
ES (1) ES472466A1 (fr)
IL (1) IL55320A (fr)
IT (1) IT1097950B (fr)

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Publication number Priority date Publication date Assignee Title
US4325729A (en) * 1977-12-13 1982-04-20 Ciba-Geigy Corporation Herbicidal and plant growth regulating pyridyloxy-phenoxy-propionic acid derivatives
US4525202A (en) * 1981-08-24 1985-06-25 Stauffer Chemical Co. Phosphonium salts of N-phosphonomethylglycine and their use as herbicides and plant growth regulants
US4341549A (en) * 1981-08-24 1982-07-27 Stauffer Chemical Company Phosphonium salts of N-phosphonomethylglycine and their use as herbicides and plant growth regulants
US5411944A (en) * 1981-11-05 1995-05-02 Union Oil Company Of California Glyphosate-sulfuric acid adduct herbicides and use
US5116401A (en) * 1981-11-05 1992-05-26 Union Oil Company Of California Herbicide and method with the glyphosate-urea adduct of sulfuric acid
US4509970A (en) * 1981-12-17 1985-04-09 Zoecon Corporation Substituted phenylphosphinyloxy- and phosphinylthio-iminocarboxylates useful for the control of weeds
US4439373A (en) * 1982-12-27 1984-03-27 Stauffer Chemical Company Process for preparing phosphonomethylated amino acids
FR2560198B1 (fr) * 1984-02-23 1987-05-07 Rhone Poulenc Agrochimie Esters de la famille de la n-phosphonomethylglycine et leur utilisation pour la preparation d'herbicides connus
ES534413A0 (es) * 1983-07-27 1986-01-01 Rhone Poulenc Agrochimie Procedimiento de preparacion de sulfonamidas con grupo ansinometilfosfonico
US4568432A (en) * 1984-12-28 1986-02-04 Monsanto Company Process for preparing glyphosate and glyphosate derivatives
FR2590901B1 (fr) * 1985-12-04 1988-07-29 Rhone Poulenc Agrochimie Procede de preparation de n-sulfonyl n-(phosphonomethyl-glycyl) amines utilisables comme herbicides
DE3721285A1 (de) * 1987-06-27 1989-01-12 Hoechst Ag Verfahren zur herstellung von n-phosphonomethylglycin
US5221659A (en) * 1991-10-28 1993-06-22 Union Oil Company Of California Plant control composition and methods of use
US5238905A (en) * 1991-10-28 1993-08-24 Union Oil Company Of California Plant control composition and methods of use with thidiazuron and monocarbamide dihydrogen sulfate
US5180846A (en) * 1991-11-06 1993-01-19 E. I. Du Pont De Nemours & Company Hydrogenation of enzymatically-produced glycolic acid/aminomethylphosphonic acid mixtures
PE20141468A1 (es) 2010-12-21 2014-11-05 Bayer Cropscience Lp Mutantes tipo papel de lija de bacillus y metodos de uso de los mismo para mejorar el crecimiento vegetal, promover la salud de plantas y controlar enfermedades y plagas
US10543481B2 (en) 2011-08-19 2020-01-28 Trustees Of Princeton Univesity Targeted, metal-catalyzed fluorination of complex compounds with fluoride ion via decarboxylation
BR112014005654A2 (pt) 2011-09-12 2017-03-28 Bayer Cropscience Lp métodos para melhorar a saúde e promover o crescimento de uma planta e/ou de melhorar o amadurecimento da fruta

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US3160632A (en) * 1961-01-30 1964-12-08 Stauffer Chemical Co Aminomethylenephosphinic acids, salts thereof, and process for their production
CH475287A (de) * 1965-10-27 1969-07-15 Monsanto Co Verfahren zur Herstellung von substituierten Aminomethylphosphinsäuren
US3853530A (en) * 1971-03-10 1974-12-10 Monsanto Co Regulating plants with n-phosphonomethylglycine and derivatives thereof
US3988142A (en) * 1972-02-03 1976-10-26 Monsanto Company Increasing carbohydrate deposition in plants with N-phosphono-methylglycine and derivatives thereof
US3894861A (en) * 1973-05-21 1975-07-15 Procter & Gamble Grass growth control compositions

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IT1097950B (it) 1985-08-31
IL55320A (en) 1982-05-31
EP0000767A1 (fr) 1979-02-21
IL55320A0 (en) 1978-10-31
IT7826674A0 (it) 1978-08-10
ES472466A1 (es) 1979-03-16
US4233056A (en) 1980-11-11
JPS5430117A (en) 1979-03-06
DE2860342D1 (en) 1981-02-12
CA1118784A (fr) 1982-02-23

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