DE10127936A1 - New organophosphorous-substituted hydroxamic acid compounds, useful as pre- or post-emergence selective herbicides in crops such as rice - Google Patents

Abstract

Organophosphorus-substituted hydroxamic acid compounds (e.g. phosphonomethyl-glycine hydroxamic acid derivatives and analogs) (I) are new. Hydroxamic acid compounds of formula (I) and their salts, esters, amides and ester salts are new. A = CR5R6, CR5R6CH(OH), CR5R6CO or COCR5R6; R1 = H; alkyl, alkenyl, alkynyl, aryl, acyl, cycloalkyl, alkyl-cycloalkyl, aralkyl, heterocyclyl or alkyl-heterocyclyl (all optionally substituted); or a Group I-III metal, optionally substituted ammonium or ammonium derived from ethylene diamine or an aminoacid; R2-R7 = H; alkyl, alkenyl, alkynyl, aryl, acyl, cycloalkyl, alkyl-cycloalkyl, aralkyl, heterocyclyl or alkyl-heterocyclyl (all optionally substituted); or benzenesulfonyl; provided that at least one of R2, R3, R5 and R7 is other than H if A = CH2; R8, R9 = H; alkyl, alkenyl, alkynyl, aryl, acyl, cycloalkyl, alkyl-cycloalkyl, aralkyl, heterocyclyl or alkyl-heterocyclyl (all optionally substituted); or OX8 or OX9; X8, X9 = as R1; the optionally substituents are Ph, OH, oxo, CN, amino (optionally substituted by 1 or 2 1-9C groups), NO2 (for cyclic groups only) or COOH (for R2 only).

Description

The invention relates to organophosphorus hydroxamic acid derivatives and their salts, Esters and amides, their use as herbicides and a process for the selective pre- or post-emergence weed control in crops.

Phosphonomethylglycylhydroxamic acid and its salts are already in the European Union patent with publication number 0 039 310. This ver Bindings show a herbicidal activity, but not for all applications enough.

The object of the present invention is therefore to provide substances with improved herbi to provide cider effectiveness.

This object is achieved by the group of substances defined in claim 1. Next education is defined by the subclaims.

The organophosphorus compounds according to the invention correspond to the general formula (I):

in which A is selected from the group consisting of -CR ₅ R ₆ -, -CR ₅ R ₆ CH (OH) -, -CR ₅ R ₆ CO- and -COCR ₅ R ₆ -,
in which R ₁ is selected from the group consisting of hydrogen, substituted and unsubstituted alkyl, substituted and unsubstituted alkenyl, substituted and unsubstituted alkynyl, substituted and unsubstituted aryl, substituted and unsubstituted aryl, substituted and unsubstituted acyl, substituted and unsubstituted cycloalkyl, substituted and unsubstituted ized alkyl-cycloalkyl, substituted and unsubstituted aralkyl, substituted and unsubstituted heterocyclic radical, substituted and unsubstituted alkyl heterocyclic radical, a metal of the first, second or third main group of the periodic system, ammonium, substituted ammonium and ammonium compounds, which differ from ethylenediamine or amino acids deduce exists
in which R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R _{7 are} identical or different and are selected from the group consisting of hydrogen, substituted and unsubstituted alkyl, substituted and unsubstituted alkenyl, substituted and unsubstituted alkynyl, substituted and unsubstituted aryl, substituted and unsubstituted acyl, substituted and unsubstituted cycloalkyl, substituted and unsubstituted alkyl-cycloalkyl, substituted and unsubstituted aralkyl, substituted and unsubstituted heterocyclic residue, substituted and unsubstituted alkyl-heterocyclic residue and benzenesulfonyl if there is A represents -CH ₂ -, at least one radical from R ₂ , R ₃ , R ₅ and R ₇ is selected from the group consisting of substituted and unsubstituted alkyl, substituted and unsubstituted alkenyl, substituted and unsubstituted alkynyl, substituted and unsubstituted aryl , substituted and unsubstituted acyl, substituted ert and unsubstituted cycloalkyl, substituted and unsubstituted alkylcycloalkyl, substituted and unsubstituted aralkyl, substituted and unsubstituted heterocyclic radical, substituted and unsubstituted alkyl heterocyclic radical and benzenesulfonyl,
in which R ₈ and R _{9 are the} same or different and are selected from the group consisting of hydrogen, substituted and unsubstituted alkyl, substituted and unsubstituted alkenyl, substituted and unsubstituted alkynyl, substituted and unsubstituted aryl, substituted and unsubstituted acyl, substituted and unsubstituted cycloalkyl, substituted and unsubstituted alkyl-cycloalkyl, substituted and unsubstituted aralkyl, substituted and unsubstituted heterocyclic radical, substituted and unsubstituted alkyl-heterocyclic radical, OX ₃ or OX ₄ ,
wherein X ₈ or X _{9 may be the} same or different and are selected from the group consisting of hydrogen, substituted and unsubstituted alkyl, substituted and unsubstituted alkenyl, substituted and unsubstituted alkynyl, substituted and unsubstituted aryl, substituted and unsubstituted acyl, substituted and unsubstituted cycloalkyl, substituted and unsubstituted alkylcycloalkyl, substituted and unsubstituted aralkyl, substituted and unsubstituted heterocyclic radical, substituted and unsubstituted alkyl heterocyclic radical, a metal of the first, second or third main group of the periodic table, ammonium, substituted ammonium and ammonium compounds, which are derived from ethylenediamine or amino acids,
where all groups with phenyl groups, hydroxy, oxo, halogen, CN, (C _0-9 ) (C _0-9 ) amino, C _1-9 alkyl, C _1-9 alkoxy groups and the cyclic radicals can also be substituted with nitro groups and R _{2 can} also be substituted with a carboxy group,
and their salts, esters and amides and salts of the esters.

R ₁ is preferably a hydrogen, a metal of the first, second or third main group of the periodic table, such as Na, K, Ca, Mg, Al, Cu and ammonium, substituted ammonium and ammonium compounds which are derived from ethylenediamine or amino acids.

R ₈ and R ₉ are preferably selected independently from the group consisting of hydrogen, methyl, ethyl, OX ₈ and OX ₉ , OX ₈ and OX ₉ preferably being selected from the group consisting of the first, second or third Main group of the periodic table, such as Na, K, Ca, Mg, Al, Cu as well as ammonium, substituted ammonium and ammonium compounds, which are derived from ethylenediamine or amino acids. That is, the salt compounds of the organophosphorus compounds with organic or organic bases (e.g. sodium salt, potassium salt, calcium salt, aluminum salt, ammonium salt, magnesium salt, triethylamine salt, ethanolamine salt, dicyclohexylamine salt, ethylene diamond salt, N, N'-dibenzylethylenediamine salt etc.) as well as salts with amino acids (e.g. argin salt, aspartic acid salt, glutamic acid salt etc.) and the like.

Peculiarities of the above definitions and suitable examples are given according to the following:
"Acyl" is a substituent derived from an acid, such as from an organic carboxylic acid, carbonic acid, carbamic acid or the thioic acid or imidic acid corresponding to the individual acids above, or from an organic sulfonic acid, these acids each being aliphatic, aromatic and / or include heterocyclic groups in the molecule and carbamoyl or carbamimidoyl.

Suitable examples of these acyl groups are given below.

Aliphatic acyl groups are acyl radicals derived from an aliphatic acid, which include the following:
Alkanoyl (e.g. formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, pivaloyl etc.);
Alkenoyl (e.g. acryloyl, methacryloyl, crotonoyl etc.);
Alkylthioalkanoyl (e.g. methylthioacetyl, ethylthioacetyl etc.);
Alkanesulfonyl (e.g. mesyl, ethanesulfonyl, propanesulfonyl, etc.);
Alkoxycarbonyl (e.g. methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl etc.);
Alkyl carbamoyl (e.g. methyl carbamoyl etc.);
(N-alkyl) thiocarbamoyl (e.g. (N-methyl) thiocarbamoyl etc.);
Alkyl carbamimidoyl (e.g. methyl carbamimidoyl etc.);
Oxalo;
Alkoxalyl (e.g. methoxalyl, ethoxalyl, propoxalyl etc.).

In the above examples of aliphatic acyl groups, the aliphatic Koh hydrogen part, in particular the alkyl group or the alkane radical, optionally one or more have suitable substituents, such as amino, halogen (e.g. fluorine, chlorine, bromine, etc.), Hy droxy, hydroxyimino, carboxy, alkoxy (e.g. methoxy, ethoxy, propoxy etc.), alkoxycar bonyl, acylamino (e.g. benzyloxycarbonylamino etc.), acyloxy (e.g. acetoxy, benzoyloxy etc.) and the like; are preferred aliphatic acyl radicals with such substituents e.g. B. with amino, carboxy, amino and carboxy, halogen, acylamino or the like sub to call substituted alkanoyle.

Aromatic acyl radicals are those acyl radicals which derive from an acid having a substituted or unsubstituted aryl group, where the aryl group can include phenyl, toluyl, xylyl, naphthyl and the like; suitable examples are given below:
Aroyl (e.g. benzoyl, toluoyl, xyloyl, naphthoyl, phthaloyl etc.);
Aralkanoyl (e.g. phenylacetyl etc.);
Aralkenoyl (e.g. cinnamoyl etc.);
Aryloxyalkanoyl (e.g. phenoxyacetyl etc.);
Arylthioalkanoyl (e.g. phenylthioacetyl etc.);
Arylaminoalkanoyl (e.g. N-phenylglycyl, etc.);
Arenesulfonyl (e.g. benzenesulfonyl, tosyl or toluenesulfonyl, naphthalenesulfonyl, etc.);
Aryloxycarbonyl (e.g. phenoxycarbonyl, naphthyloxycarbonyl etc.);
Aralkoxycarbonyl (e.g. benzyloxycarbonyl etc.);
Arylcarbamoyl (e.g. phenylcarbamoyl, naphthylcarbamoyl etc.);
Arylglyoxyloyl (e.g. phenylglyoxyloyl etc.).

In the above examples of aromatic acyl radicals, the aromatic hydrocarbon part (in particular the aryl radical) and / or the aliphatic hydrocarbon part (in particular the alkane radical) can optionally have one or more suitable substituents, such as those which are suitable as substituents for the alkyl group or the alkane residue have already been specified. In particular and as an example of preferred aromatic acyl radicals with particular substituents, arylanoyl substituted with halogen and hydroxy or with halogen and acyloxy and aralkanoyl substituted with hydroxy, hydroxyimino, dihalogenalkanoyloxyimino are also given
Arylthiocarbamoyl (e.g. phenylthiocarbamoyl etc.);
Arylcarbamimidoyl (e.g. phenylcarbamimidoyl etc.).

A heterocyclic acyl radical is understood to mean an acyl radical which comes from an acid with a heterocyclic group; this includes:
Heterocyclic carbonyl, in which the heterocyclic radical is an aromatic or aliphatic 5- to 6-membered heterocycle with at least one heteroatom from the group consisting of nitrogen, oxygen and sulfur (e.g. thiophenyl, furoyl, pyrrole carbonyl, nicotinoyl etc.);
Heterocycle alkanoyl, in which the heterocyclic radical is 5- to 6-membered and has at least one heteroatom from the group consisting of nitrogen, oxygen and sulfur (e.g. thiophenylacetyl, furylacetyl, imidazolylpropionyl, tetrazolylacetyl, 2- (2-amino-4 - thiazolyl) -2-methoxyiminoacetyl etc.) and the like.

In the above examples of heterocyclic acyl radicals, the heterocycle and / or the aliphatic hydrocarbon part optionally one or more suitable substituents ducks, like the same ones, indicated as being suitable for alkyl and alkane groups were.

"Alkyl" is a straight or branched chain alkyl radical with up to 18 carbon atoms toms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl and the like.

"Alkenyl" includes straight or branched chain alkenyl groups with up to 18  Carbon atoms such as B. vinyl, propenyl (e.g. 1-propenyl, 2-propenyl), 1- Methyl propenyl, 2-methyl propenyl, butenyl, 2-ethyl propenyl, pentenyl, hexenyl.

"Alkynyl" includes straight or branched chain alkynyl groups with up to 18 Carbon atoms.

Cycloalkyl preferably represents an optionally substituted C _3-7 cycloalkyl or a bi- or tricycloalkyl of C _3-7 rings; possible substituents include alkyl, alkenyl, alkynyl, alkoxy (e.g. methoxy, ethoxy etc.), halogen (e.g. fluorine, chlorine, bromine etc.), nitro and the like. A heterocyclic ring is correspondingly a cycloalkyl as defined above, in which one, two or more carbon atoms in the ring are independently replaced by oxygen, nitrogen or sulfur atoms.

Aryl is an aromatic hydrocarbon residue such as phenyl, naphthyl, etc., which may can have one or more suitable substituents, such as alkyl, alkenyl, alkynyl, Alkoxy (e.g. methoxy, ethoxy etc.), halogen (e.g. fluorine, chlorine, bromine etc.), nitro and the like same.

"Aralkyl" includes mono-, di-, triphenylalkyls such as benzyl, phenethyl, benzhy dryl, trityl and the like, the aromatic part optionally one or more suitable May have substituents such as alkoxy (e.g. methoxy, ethoxy etc.), halogen (e.g. fluorine, Chlorine, bromine, etc.), nitro and the like.

In the above ester, the alkane and / or arene part can optionally have at least one have suitable substituents such as halogen, alkoxy, hydroxy, nitro or the like.

The compounds of the formula (I) according to the invention can in their proto form as the ammonium salt of organic or inorganic acids, such as hydrochloric acid, Hydrobromic acid, sulfuric acid, nitric acid, methanesulfonic acid, p- Toluenesulfonic acid, acetic acid, lactic acid, maleic acid, fumaric acid, oxalic acid, tartaric acid, Benzoic acid, etc. are present.

The compounds of the formulas (I) used according to the invention, for example for double-containing or chiral groups R ₁ to R ₉ , X ₁ , X ₈ , X ₉ and A, allow the occurrence of spatial isomers. The compounds according to the invention include all spatial isomers both as pure substances and in the form of their mixtures.

Individual compounds which correspond to the following structural formulas are particularly preferred:

The compounds of formula I have a herbicidal action. They are suitable for. B. for the selective control of grasses in crops.

The invention relates to herbicidal active compounds of the formula I, their use and a Procedure for pre- and post-emergence weed control.

The compounds of formula I are in unchanged form or preferably as Means used together with the usual aids in formulation technology and are therefore z. B. to emulsion concentrates, directly sprayable or dilutable Lö solutions, diluted emulsions, wettable powders, soluble powders, dusts, granules, also encapsulations such. B. polymeric materials processed in a known manner. The An application processes such as spraying, atomizing, dusting, scattering or pouring just like the type of means, the desired goals and the given circumstances chosen speaking.

The formulations, i.e. H. the active ingredient of formula I and optionally a fe Most or liquid additive containing compositions, preparations or compositions are made in a known manner, e.g. B. by intimate mixing and / or grinding the active ingredients with extenders, such as. B. solvents, solid carriers, and given if necessary, surface-active compounds (surfactants).

Possible solvents are: aromatic hydrocarbons, preferably e.g. B .:
Xylene mixtures or substituted naphthalenes, phthalic esters, aliphatic hydrocarbons, such as cyclohexane or paraffins, alcohol and glycols, and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or ethylene ether, ketones, strongly polar solvents and optionally epoxidized vegetable oils or water.

As solid carriers, e.g. B. dusts and dispersible powders are in the Usually natural rock flour is used like calcite, talc, kaolin, or montmorillonite Attapulgite. To improve the physical property, finely divided grains can also be used silica or highly disperse absorbent polymers can be added. As granular, adsorb tive granulate carriers come porous types, such as. B. pumice, broken brick, sepiolite or Bentonite, as nonsorptive carrier materials e.g. B. calcite or sand in question. Furthermore can be a variety of pre-granulated materials of inorganic or organic nature, such as especially dolomite or crushed plant residues can be used.

Depending on the nature of the formulation to be formulated, suitable surface-active compounds Active ingredient of formula I nonionic, cationic and / or anionic surfactants with good Emulsifying, dispersing and wetting properties into consideration. Surfactants are also among surfactants to understand mixtures.

Suitable anionic surfactants can be both so-called water-soluble soaps also be water-soluble synthetic surface-active compounds. Also become common so-called synthetic surfactants are used, in particular fatty sulfonates, fatty sulfates, sulfo nated benzimidazole derivatives or alkylarylsulfonates.  

Corresponding phosphates are also suitable.

The primary nonionic surfactants are polyglycol ether derivatives from ali phatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and Alkylphenols in question, the 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (Aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical or Al may contain kylphenols.

Other suitable nonionic surfactants are the water-soluble, 20 to 250 ethyl glycol ether groups or polyethylene containing 10 to 100 propylene glycol ether groups Lenoxide adducts with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypro pylene glycol with 1 to 10 carbon atoms in the alkyl chain. The connections mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit.

Fatty acid esters of polyoxyethylene sorbitan such as polyoxy can also be used ethylene sorbitan trioleate into consideration.

The cationic surfactants are primarily quaternary ammonia salts, which ent as N-substituents at least one alkyl radical having 8 to 22 carbon atoms hold and as further substituents low, optionally halogenated alkyl, benzyl or have lower hydroxyalkyl radicals. The salts are preferably in the form of halides Methyl sulfates.

The active substance preparations generally contain 0.1 to 95%, in particular 0.1 to 80%, active ingredient of the formula I, 1 to 99.9% of a solid or liquid additive and 0 to 25% in particular 0.1 to 25% of a surfactant.

In particular, preferred formulations are composed as follows:
(% = Weight percent).

Emulsifiable concentrates

Active ingredient: 1 to 20%, preferably 5 to 10%
Surfactants: 5 to 30%, preferably 10 to 20%
Liquid carrier: 50 to 94%, preferably 10 to 85%.

Dusts

Active ingredient: 0.1 to 10%, preferably 0.1 to 1%
Solid vehicle: 99.9 to 90%, preferably 99.9 to 99%.

Suspension concentrate

Active ingredient: 5 to 75%, preferably 10 to 50%
Water: 94 to 25%, preferably 90 to 30%
Surfactant: 1 to 40%, preferably 2 to 30%.

Wettable powder

Active ingredient: 0.5 to 90%, preferably 1 to 80%
Surfactant: 0.5 to 20%, preferably 1 to 15%
Solid vehicle: 5 to 95%, preferably 10 to 90%.

Granules

Active ingredient: 0.5 to 30%, preferably 3 to 15%
Solid vehicle: 99.5 to 70%, preferably 97 to 85%.

While concentrated agents are preferred as a commercial product, are used the end user usually diluted means. The application forms can go down be diluted to 0.001% of active ingredient. The amount of effort is usually 0.001 up to 10 kg / ha, preferably 0.025 to 5 kg / ha.

The agents can also contain other additives such as stabilizers, defoamers, viscosi efficiency regulators, binders, adhesives as well as fertilizers or other active ingredients to achieve this special effects included.

Basically, the expert knows which synthetic route he uses to produce the substances to choose according to the invention. In the following, some syn thesis routes for compounds of the invention are given.

Synthesis examples

Synthetic routes for appearance connections:
HO-NR ¹ -CO-CHR ² -NR ³ -CHR ⁴ -P (= O) (OH) ₂
with R ¹ = R ² = R ³ = H and R ⁴ = n-butyl: 1
with R ¹ = R ² = H, R ³ = methyl and R ⁴ = m-pyridyl: 2
with R ¹ = R ² = H, R ³ = n-butyl and R ⁴ = methyl: 3
with R ¹ = R ² = R ³ = H and R ⁴ = methyl, ethyl: 4
with R ¹ = R ⁴ = H, R ² = methyl and R ⁴ = methyl: 5
with R ¹ = H, R ² = R ³ = R ⁴ = methyl: 6
with R ¹ = methyl, R ² = R ³ = R ⁴ = H: 7
with R ¹ = isopropyl, R ² = R ³ = R ⁴ = H: 8

N- (1-phosphonopentyl) glycine hydroxamate (1)

N-pentylidene glycine methyl ester 1a

2.51 g (20 mmol) glycine methyl ester hydrochloride are mixed with 2.42 g (24 mmol) Triethylamine and 2.58 g (30 mmol) freshly distilled pentanal - and to dissolve with the minimal volume of water - added. The mixture is stirred for 3 d in the dark at RT and extracted with Ether, washes the combined extracts with water and concentrated under reduced pressure. Man receives Imin 1a as a brownish oil in a satisfactory yield, which without additional Cleaning is implemented further.

N- (1-phosphonopentyl) glycine methyl ester 1b

A mixture of 1.88 g (12 mmol) imine 1a and 0.98 g (12 mmol) phosphorous Acid are heated to 110 ° C. After 10 min at a reaction temperature of 150 ° C is cooled to 90 ° C., 10 ml of 50% aqueous ethanol are added, the product 1b is obtained as a white solid in a satisfactory yield on further cooling.

N- (1-phosphonopentyl) glycine hydroxamate (1)

The reaction of 1.19 g (5 mmol) of phosphonic acid 1b with 30 mmol of free Hy droxylamine in 50 ml aqueous methanol with the addition of 3.8 ml (15 mmol) 4-M-NaOH- Solute delivers overnight after stirring, concentrate on a rotary evaporator and clean on one Anion exchange column hydroxamic acid 1 as a colorless solid in moderate yield.

N-methyl-N - [(3-pyridyl) phosphonomethyl] glycine hydroxamate (2)

N-methyl-N - [(3-pyridyl) phosphonomethyl] glycinamide 2a

2.02 g (10 mmol) 1- (N-methylamino) -1- (3-pyridyl) methylphosphonic acid (after B. Boduszek, J. S. Wieczorek, J. Prakt. Chemie 328, 627 (1986)) are mixed with 0.84 g (10 mmol) Sodium bicarbonate dissolved in 30 ml of water. After entry of 0.94 g (10 mmol) 2- Chloroacetamide is allowed to stir overnight and the suspension is then heated for 1 h Reflux. The resulting almost clear solution is filtered hot. The filtrate is under right reduced pressure, the residue taken up in a little water and with half-conc. aqueous HCl adjusted a pH of 4-5. The acid amide 2a is removed from the solution with acetone fallen out and implemented without cleaning step.

N-methyl-N - [(3-pyridyl) phosphonomethyl] glycine hydroxamate (2)

0.50 g of the crude product 2a with 0.15 g (2.2 mmol) of hydroxylamine hydrochloride rid dissolved in 5 ml of water. After 5 d at RT, the mixture is diluted with water and the product is 2 in poor yield at the anion exchanger cleaned.  

N-butyl-N- (1-phosphono-ethyl) glycine hydroxamate (3)

N-ethylidene glycine methyl ester 3a

Reaction of 6.28 g (50 mmol) of glycine methyl ester hydrochloride with 3.30 g (75 mmol) acetaldehyde analogous to imine 1a gives the crude imine 3a in good yield.

N- (1-phosphonoethyl) glycine methyl ester 3b

Reaction of 4.37 g (38 mmol) of crude imine 3a with 3.12 g (38 mmol) of phosphorous Acid analogous to compound 1b provides aminomethanephosphonic acid 3b as almost colorless Solid in medium yield.

N-butyl-N- (1-phosphono-ethyl) glycine methyl ester 3c

3.94 g (20 mmol) 3b are mixed with 2.74 g (20 nimol) n- Butyl bromide implemented. As a product, 3c falls into a mixture of the methyl and butyl esters Form of a yellowish powder in low yield.

N-butyl-N- (1-phosphono-ethyl) glycine hydroxamate (3)

A suspension of 0.40 g (1.5 mmol) 3c in 15 ml of absolute methanol is added 8.0 mmol free hydroxylamine in methanol and 0.10 g (4.5 mmol) sodium in 20 ml abs. Methanol added. After stirring overnight at RT, the mixture is concentrated and the semi-solid is washed Residue several times with acetone. After taking up the now solid residue in 5 ml of what it is made with a half-conc. HCl a pH of 5 to 6 and the product falls through Add acetone. Hydroxamic acid 3 is a colorless solid in moderate yield hold.

N- (1-phosphono-1-methylpropyl) -L-alanine hydroxamate (4)

N- (1-phosphono-1-methylpropyl) -L-alaninamide 4a

1.53 g (10 mmol) of 1-amino-1-methyl-propylphosphonic acid (according to M. Soroka, Liebigs Ann. Chem. 1990, 331) with 0.98 g (10 mmol) chloroacetamide to N- (1-phosphono-1- methylpropyl) alaninamide 4a implemented. After precipitation from water / acetone, 4a Recrystallization from water / acetone obtained in good yield pure.

N- (1-phosphono-1-methyl-propyl) -L-alanine hydroxamate (4)

1.57 g (7.5 mmol) of 4a are mixed with 0.52 g (7.5 mmol) of hydroxylamine hydrochloride little water dissolved. After 7 d at RT, the mixture is diluted with water and the product 4 on anio exchangers cleaned. N- (1-Phosphono-1-methylpropyl) -L-alanine hydroxamate is obtained 4 in moderate yield as a pale yellow solid.

N-methyl-N-phosphonomethyl-L-alanine hydroxamate (5)

N-methyl-N-phosphonomethyl-L-alanine 5a

1.03 g (10 mmol) of N-methyl-L-alanine are mixed with 2.46 g (30 mmol) in 10 ml of water. phosphorous acid and 10 ml conc. HCl heated to reflux. 15 ml become within 15 min 37% formalin solution. added dropwise and heated under reflux for a further hour. After this When cooling, crystals precipitate, which are filtered and washed with isopropanol. Umkri stallize from water / isopropanol provides colorless crystals of 5a in medium yield.

N-methyl-N-phosphonomethyl-L-alanine hydroxamate (5)

1.18 g (6 mmol) 5a are p- in 50 ml of absolute ethanol with a spatula tip Toluene sulfonic acid suspended. After refluxing for 5 hours, the solution concentrated under reduced pressure, the oily residue dissolved in 25 ml of absolute methanol and a solution of 30 mmol hydroxylamine in methanol added dropwise [from 2.08 g (30 mmol) Hydroxylamine hydrochloride and sodium methoxide in equimolar amounts]. To the resulting suspension is added 0.41 g (18 mmol) sodium in methanol. After stirring The solvent is removed overnight under reduced pressure and taken up in water and separates product 5 from other salts in moderate yield on an anion exchanger from.  

N-methyl-N- (1-phosphono-ethyl) -L-alanine hydroxamate (6)

N-ethylidene-L-alanine methyl ester 6a

The reaction of 6.98 g (50 mmol) of L-alanine methyl ester with 3.30 g (75 mmol) Acetaldehyde according to the instructions for compound 1a gives the crude imine 6a in good yield.

N- (1-phosphonoethyl) -L-alanine methyl ester 6b

The reaction of 4.51 g (35 mmol) of crude imine 6a with 2.87 g (35 mmol) of phosphori ger acid according to the instructions for 1a provides the aminomethanephosphonic acid 1b as colorless Solid in medium yield.

N-methyl-N- (1-phosphono-ethyl) -L-alanine methyl ester 6c

3.17 g (15 mmol) 6b are suspended in 50 ml of peroxide-free THF. This suspension is successively mixed with 5.0 g of anhydrous K ₂ CO ₃ , 5 drops of 18-crown-6, 0.5 g of Bu ₄ NI and 2.18 g (15 mmol) of MeI. After stirring overnight at 30 ° C., the mixture is cooled to 0 ° C. and filtered. The filter residue is taken up in water. The product precipitates when acetone is added. 6c is obtained as a yellowish solid in moderate yield.

N-methyl-N- (1-phosphono-ethyl) -L-alanine hydroxamate (6)

A solution of 0.90 g (4 mmol) 6c in 15 ml water is washed with a methanolic Solution of 20 mmol free hydroxylamine and mixed with 3.0 ml (12 mmol) 4-M-NaOH. After 1 h the hydroxamate 6 is an almost colorless solid in medium yield by Rei isolated on the anion exchanger.

(N-phosphonomethylglycine) -N-methylhydroxamate (7)

1.50 g (8.8 mmol) of N-phosphonomethylglycine is placed in 80 ml of absolute ethanol Add 3 drops of conc. Sulfuric acid refluxed for 3 h. After cooling, set 10 Equivalents of an equimolar mixture of N-methylhydroxylamine hydrochloride and NaOH in water, stir for 20 min and then adjust the pH to 13. The resulting low  Blow is collected, dissolved in water, adjusted to pH 8 with HCl and over an anion dew shear column cleaned. The desired hydroxamate 7 is obtained in medium yield.

(N-phosphonomethylglycine) -N-isopropylhydroxamate (8)

The connection 8 is represented analogously to the production of the connection 7 by reacting N-phosphonomethylglycine with N- Isopropylhydroxylamine hydrochloride. Compound 8 is obtained in low yield ten.

The herbicidal activity of the verb according to the invention is also described below described:

Fabric: 1

Fabric: 2

Fabric: 3

Fabric: 4

Fabric: 5

Fabric: 6

Fabric: 7

Fabric: 8

Claims (8)

1. Organophosphorus compounds of the general formula (I):
in which A is selected from the group consisting of -CR ₅ R ₆ -, -CR ₅ R ₆ CH (OH) -, -CR ₅ R ₆ CO- and -COCR ₅ R ₆ -,
wherein R ¹ is selected from the group consisting of hydrogen, substituted and unsubstituted alkyl, substituted and unsubstituted alkenyl, substituted and unsubstituted alkynyl, substituted and unsubstituted aryl, substituted and unsubstituted aryl, substituted and unsubstituted acyl, substituted and unsubstituted cycloalkyl, substituted and unsubstituted alkyl -Cycloalkyl, substituted and unsubstituted aralkyl, substituted and unsubstituted heterocyclic radical, substituted and unsubstituted alkyl heterocyclic radical, a metal of the first, second or third main group of the periodic table, ammonium, substituted ammonium and ammonium compounds derived from ethylenediamine or amino acids , consists,
in which R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R _{7 are the} same or different and are selected from the group consisting of hydrogen, substituted and unsubstituted alkyl, substituted and unsubstituted alkenyl, substituted and unsubstituted alkynyl , substituted and unsubstituted aryl, substituted and unsubstituted acyl, substituted and unsubstituted cycloalkyl, substituted and unsubstituted alkylcycloalkyl, substituted and unsubstituted aralkyl, substituted and unsubstituted heterocyclic radical, substituted and unsubstituted alkyl and heterocyclyl radical and benzene when A is -CH ₂ - at least one radical from R ₂ , R ₃ , R ₅ and R ₇ is selected from the group consisting of substituted and unsubstituted alkyl, substituted and unsubstituted alkenyl, substituted and unsubstituted alkynyl, substituted and unsubstituted aryl, substituted and unsubstituted acyl, subs substituted and unsubstituted cycloalkyl, substituted and unsubstituted alkyl-cycloalkyl, substituted and unsubstituted aralkyl, substituted and unsubstituted heterocyclic radical, substituted and unsubstituted alkyl-heterocyclic radical and benzenesulfonyl,
in which R ₈ and R _{9 are the} same or different and are selected from the group consisting of hydrogen, substituted and unsubstituted alkyl, substituted and unsubstituted alkenyl, substituted and unsubstituted alkynyl, substituted and unsubstituted aryl, substituted and unsubstituted acyl, substituted and un substituted cycloalkyl, substituted and unsubstituted alkyl-cycloalkyl, substituted and unsubstituted aralkyl, substituted and unsubstituted heterocyclic radical, substituted and unsubstituted alkyl-heterocyclic radical, OX ₃ or OX ₄ ,
wherein X ₈ or X _{9 may be the} same or different and are selected from the group consisting of hydrogen, substituted and unsubstituted alkyl, substituted and unsubstituted alkenyl, substituted and unsubstituted alkynyl, substituted and unsubstituted aryl, substituted and unsubstituted acyl, substituted and unsubstituted Cycloalkyl, substituted and unsubstituted alkyl-cycloalkyl, substituted and unsubstituted aralkyl, substituted and unsubstituted heterocyclic radical, substituted and unsubstituted alkyl-heterocyclic radical, a metal of the first, second or third main group of the periodic table, ammonium, substituted ammonium and ammonium compounds derived from ethylenediamine or amino acids,
where all groups with phenyl groups, hydroxyl, oxo, halogen, CN, (C _0-9 ) (C _0-9 ) amino, C _1-9 alkyl, C _1-9 alkoxy groups and the cyclic radicals can also be substituted with nitro groups and R ₂ also with a carboxy group,
and their salts, esters and amides and salts of the esters. 2. Compounds according to claim 1, characterized in that R _{1 is selected} from the group consisting of hydrogen, a metal of the first, second or third main group of the periodic table, such as Na, K, Ca, Mg, Al, Cu and Ammonium, substituted ammonium and ammonium compounds derived from ethylenediamine or amino acids. 3. Compounds according to claim 1 or 2, characterized in that R ₈ and R _{9 are} independently selected from the group consisting of hydrogen, methyl, ethyl, OX ₈ and OX ₉ . 4. Compounds according to claim 3, characterized in that OX ₈ and OX ₉ are selected from the group consisting of the first, second or third main group of the peri od system, such as Na, K, Ca, Mg, Al, Cu and ammonium, substituted ammonium and ammonium compounds derived from ethylenediamine or amino acids. 5. Compounds according to claim 1, characterized in that they are selected from the group consisting of
consists. 6. Use according to claim 5, characterized in that the compounds from the Are selected from N- (1-phosphonopentyl) glycine hydroxamate, N-methyl N - [(3-pyridyl) phosphonomethyl] glycine hydroxamate, N-butyl-N- (1-phosphonoethyl) - glycine hydroxamate, N- (1-phosphono-1-methylpropyl) -L-alanine hydroxamate, N-methyl- N-phosphonomethyl-L-alanine hydroxamate, N-methyl-N- (1-phosphonoethyl) -L- alanine hydroxamate, N-phosphonomethylglycine-N-methylhydroxamate and (N- Phosphonomethylglycine) -N-isopropylhydroxamate. 7. Use of organophosphorus compounds according to one of claims 1 to 6 as a herbicide. 8. Procedure for selective pre- or post-emergence control of weeds in Crop crops, characterized in that the crops or their Cultivated area with an effective amount of at least one of the claims 1 to 6 defined compounds according to formula (1) or at least one such Treated compound containing agent.