DD252753A5 - MEDIUM FOR WEEDING - Google Patents

Abstract

The invention relates to weed killing agents. According to the invention, di- and tripeptides with N-terminal phosphinothricin of the formula (I) in which phosphinothricin is linked with 1 or 2 molecules of preferably natural amino acids are used as the active ingredient in the novel herbicidal compositions. In formula I, R 1 is hydrogen or (C 1 -C 12) -alkyl, R 2 and R 4 independently of one another are hydrogen, (C 1 -C 12) -alkyl, (C 3 -C 8) -cycloalkyl, phenyl or phenyl (C 1 -C 2) -alkyl, wherein said groups in turn may be substituted by halogen, NH 2, OH, SH, NO 2, CF 3, (C 1 -C 4) alkoxy, (C 1 -C 4) alkylthio, (C 1 -C 4) alkoxycarbonyl, COOH or CONH 2, R 3 and R 3 R5 is hydrogen or methyl, n0 or 1, ando and p independently of one another 0, 1, 2 or 3. Formula (I)

Description

Field of application of the invention

The invention relates to weed control compositions containing di- and tripeptides with N-terminal phosphinothricin.

The compositions according to the invention are used in agriculture for controlling undesired plant growth.

Characteristic of the known state of the art

It is known that the phosphinothricin (Ptc) 0

P-CH ₀ -CH ₀ -CH-COOH HO

and some of its peptides have good herbicidal activity. Of the latter, H-Ptc-Gly-OH and H-Ptc-Ala-OH (JA-Sho-55-7237) have already been described; H-Ptc-Ala-Ala-OH (bialaphone or SF-1293, DE-AS 2236599 and DE-PS 2848224), H-Ptc-Ala-Leu-OH (J.Antibiotic., 37, 829 [1984]) and a number of other N -terminal Ptc tripeptides (JA-A Sho-60-222498). A number of dipeptides with N-terminal Ptc is also formally included in the claim of DE-PS 2717440. In the patent, however, neither examples of dipeptides are mentioned nor given a method for their preparation. The previously known methods of synthesis are tedious and have so far been carried out only on a small scale. This is due to the phosphinyl group of the Ptc, which must be protected in the conventional methods, otherwise side reactions occur that severely affect the yield and purity of the final products.

Object of the invention

The aim of the present invention is to provide novel, herbicidally active di- and tripeptides with N-terminal Ptc, which are suitable for controlling undesired plant growth in agricultural crops and for total weed control.

Explanation of the essence of the invention

The invention has for its object to find new compounds with the desired properties that are suitable as an active ingredient in weed control agents.

According to the invention compounds of the general formula I are used as active ingredient in the new weed control agents,

H ₅ C "(Γ / R ^ _R 5

P-CH ₀ CH ₀ -CH-CO-T-NH-C- (CH ₀₎ -CO-I-NH-C (CH ₅₎ -COOR ₁ (I) H0 ^/ NH ₂ \ R ^ / _n R ^

R ^{1 is} hydrogen or (C ¹ -C ₁₂ ) -alkyl,

R ² and R ⁴ independently of one another are hydrogen, (C 1 -C ₁₂ ) -alkyl, (C 1 -C 15 -cycloalkyl, phenyl or phenyl (C 1 -C ₂ ) -alkyl, where the groups mentioned are themselves represented by halogen, NH ₂ , OH, SH, NO ₂ , CF ₃ (C ₁ -C ₄ -alkoxy, (C ₁ -C ₄ ) -alkylthio, (C ₁ -C ₄ ) -

Alkoxycarbonyl, COOH or CONH ₂ can be substituted, R ³ and R ^{5 are} hydrogen or methyl, η is 0 or 1 and ο and ρ are independently of each other 0,1,2 or 3, except compounds in which

a) η = O, R ⁴ = H or CH ₃ and R ⁵ = H; or

b) η = 1, R ³ and R ⁵ = H and R ² and R ⁴ = H, CH ₃ , C ₂ H ₅ , CH (CH ₃ J ₂ or CH ₂ OH;

c) η = 1, R ³ and R ⁵ = H, R ² = CH ₃ and R ⁴ = CH ₂ CH (CH ₃ J ₂₎ , and their salts with bases or acids.

Depending on the substitution, the compounds of the formula I contain 1, 2 or 3 asymmetric carbon atoms. They can therefore occur in several stereoisomeric forms. The invention therefore relates not only to the racemates of the formula I, but also their stereoisomers and mixtures thereof in any ratios.

Preferred compounds are those in which

R ^{1 is} hydrogen or (C ¹ -C ₈ ) -alkyl,

R ² and R ⁴ independently of one another are H, (d-Celalkyl, (C ₃ -C ₄ ) -aminoalkyl, hydroxyethyl, thiomethyl, methylthioethyl, carboxymethyl or -ethyl, carbamoylmethyl or -ethyl, carbo (d-CJ-alkoxymethyl or -ethyl Phenyl, benzyl or

Hydroxybenzyl, R ³ and R ^{6 are} H or CH ₃ , η 0 or 1, and

ο and ρ independently of one another denote 0.1 or 2 (excluding the compounds listed under a), b) and c) above, and salts thereof.

Particularly preferred are those compounds in which Ptc with "natural", ie proteinogenic amino acids such as alanine (Ala), a-aminobutyric acid (Abu), asparagine (Asn), aspartic acid (Asp), cysteine (Cys), glutamine (GIn), Glutamic acid (GIu), glycine (GIy), isoleucine (Me), leucine (Leu), lysine (Lys), methionine (Met), ornithine (Om), phenylalanine (Phe), serine (Ser), threonine (Thr), Tyrosine (Tyr), valine (VaI) or non-proteinogenic amino acids such as phenylglycine (Phg) or norvaline (Nva) is one or two times N-terminally linked.

Since the compounds of formula I contain acidic (-COOH, -P- (O) OH) and basic (-NH ₂ ) groups, they are capable of salting with bases and strong acids. Suitable salts with bases are in particular the alkali and alkaline earth salts (with Na ⁺ , K ⁺ or Ca ⁺⁺ ), ammonium salts and salts with organic ammonium bases such as mono-, di and Tn-BIlCyI- (C ₁ -C ₄ ) - or Hydroxyethylammoniumsalze, further the benzyl, dibenzyl, phenyl, diphenyl and Dicyclohexylammoniumsalze into consideration. Particularly suitable acids for forming salts on the amino group are HCI, HBr, H ₂ SO ₄ , HNO ₃ , H ₃ PO ₄ , HCIO ₄ and benzenesulfonic acid.

The invention also provides a process for the preparation of the compounds of the general formula I which is characterized in that a compound of the formula II

H, CO ·> N Ii

P-CH ₂ -CH ₂ -CH-CO ₂ H <»>

HO NHA

wherein A is an amino-protecting group, with the salt of an amino acid or. Dipeptide derivatives of the formula III,

i? ' ) F 6

H ^ N-f-C-C'ONH - / - C-COOR (Mi)

² U ² ..7>

wherein Ft6 is a common in peptide chemistry carboxyl protecting group such as lower alkyl or benzyl, in the presence of a base and a dialkylcarbodiimide such as dicyclohexylcarbodiimide (DCC) as a condensing agent and then, if desired, cleaves the protective groups present.

Suitable components III are, above all, the salts of the natural amino acids because of their ready accessibility.

As far as the starting materials are not commercially available substances, they can be prepared by literature methods. Suitable salts of III are in particular the hydrochlorides, but also salts with other strong acids in question. The protecting groups on II are those customary in peptide chemistry; for example, the carbobenzoxy (Cbo-) group and tert. Butyloxycarbonyl (Boc) group called. The condensation of the two components is conveniently carried out in an inert solvent such as CH ₂ Cl ₂ , dioxane, tetrahydrofuran, ethyl acetate, dimethoxyethane, acetonitrile or dimethylformamide at temperatures between -2O ⁰ C and 6O ⁰ C, preferably between -10 ° Cund50 ° Cin the presence an auxiliary base and a dialkylcarbodiimide, e.g. B. dicyclohexylcarbodiimide, from. Suitable auxiliary bases are tertiary organic amines such as triethylamine, N-ethylmorpholine or pyridine.

After the peptide linkage remain protecting groups in the molecule, which can be cleaved by literature methods, e.g. the Cbo group and the ßenzylgruppe by hydrogenolysis, the Boc group by acidolysis, alkyl ester groups by acidic or alkaline hydrolysis.

Depending on the nature and sequence of the deprotection, the compounds I according to the invention are obtained in free form or as salts. The salts can be converted into the free peptides by methods known from the literature (for example by reaction of the hydrochlorides with propylene oxide). From these salts are obtained by titration with one equivalent of acid or base and evaporation of the aqueous solution.

A particular advantage of the production process according to the invention is that it is possible to dispense with a masking of the phosphinic acid function. Although the latter might well be able to react with the condensing agent, the formation of the peptide compound proceeds uniformly via the carobxyl function.

The erfindungsgeläßen compounds of formula I have excellent herbicidal activity against a broad spectrum of economically important monocotyledonous and dicotyledonous harmful plants. Hard-to-control perennial weeds, which sprout out of rhizomes, rhizomes or other permanent organs, are well detected by the active ingredients. It does not matter whether the substances are applied in the pre-sowing, pre-emergence or postemergence process.

The compounds of formula I can be combined with numerous other herbicides; the mixtures have partially synergistic effect. Examples of such mixture partners are:

Triazines such as 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine (atrazine), 2-chloro-4,6-bis (ethylamino) -1,3,5-triazine (simazine), 2 tert-butylamino-4-chloro-6-ethylamino-1,3,5-triazine (terbutylazine), 2-tert-butylamino-4-ethylamino-6-methoxy-1,3,5-triazine ( Terbumone), 2-ethylamino-4-isopropylamino-6-methylthio-1,3,5-triazine (ametryne), 2,4-bis (isopropylamino) -6-methylthio-1,3,5-triazine (prometry) or 2-tert-butylamino-ethylamino-e-methylthio-IAB-triazine (Terbutryne), growth promoters such as 2,4-dichlorophenoxyacetic acid (2,4-D), 4-chloro-2-methylphenoxyacetic acid (MCPA), 4-chloro 2-methylphenoxypropionic acid (CMPP), 2- (2,4-dichlorophenoxy) -propionic acid (2,4-DP), 2,4,5-trichlorophenoxyacetic acid (2,4,5-T), 3,6-dichloro-2 methoxybenzoic acid (Dicamba) and their esters and salts,

Acetanilides such as 2-chloro-2 ', 6'-diethyl-N-methoxymethylacet-anilide alachlor, 2-chloro-6'-ethyl-N- (2-methoxy-1-methyl-ethyl) -aceto-toluidol metolachlor, or 2-Chloro-N- (ethoxy-methyl) -6'-ethylacet-o-toluidide, phenylurea such as S-fSi-dichlorophenyl-i-methoxy-i-methylurea (Linuron), 3- (3,4-dichlorophenyl) -1 , 1-dimethylurea (diuron), 3- (4-chlorophenyl) -1-methoxy-1-methylurea (monolinuron), also 2- [3- (4,6-dimethylpyrimidin-2-yl) ureidosulfonyl] -benzoic acid methyl ester, 2 - (4-Isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl-nicotinic acid isopropylammonium salt, 2- (4-isopropyl) -4-methyl-5-oxo-2-imidazolin-2-yl) quinoline-3-carboxylic acid, methyl 2- [3- (4-chloro-e-methoxypyrimidine) -YO-ureidosulfonylbenzoate, 4-amino-6-tert-butyl-4,5-dihydro-3-methylthio-1, 2,4-triazin-5-one, 3-amino-1H-1,2,4-triazole, 2,6-dinitro-N, N-dipropyl-4-trifluoromethylaniline (trifluralin), ammonium ethylcarbamoylphosphonate and N- (phosphonomethyl ) glycine (glyphosate).

Upon application of the active ingredients to the green plant parts postemergence, a drastic halt in growth occurs very rapidly after the treatment, and the weed plants remain in the growth stage present at the time of application and after a certain period die more or less rapidly, so that in this way a weed competition harmful to crops can be eliminated very early and sustainably by the use of the novel agents of the invention.

The compounds of the invention also have an excellent and very broad activity against a wide range of annual and perennial weeds and weeds growing on roadsides, in industrial or railway plants. The active ingredients are therefore suitable both for use on non-agricultural land as well as for weed control in agriculture. The use of non-selective compounds in one or more agricultural crops is possible, provided that the nature of the application and / or the age of the crop ensures that the crops or their delicate green parts are not sprayed and thus suffer no harm. Examples of such applications are plantations, tree crops, vineyards, etc.

Since application of the new compounds does not cause damage to the one-year crops prior to emergence of the crops or in their ripening stage, they can also be used prior to sowing, shortly before or after harvest in the course of minimal tillage, the control of late transplantation and harvest relief.

The invention therefore also provides herbicidal compositions which contain the compound of the formula I and their use for controlling unwanted plant growth.

The agents according to the invention contain the active compounds according to the general formula I to 2-95%. Since the active ingredients are partially water-soluble, they can be used advantageously as aqueous solutions. Otherwise, they can be used as emulsifiable concentrates, wettable powders and sprayable solutions in the usual preparation forms, unless they themselves are water-soluble.

Wettable powders are preparations which are uniformly dispersible in water and which, in addition to the active ingredient, also contain wetting agents, in addition to a diluent or inert substance, e.g. Polyoxethylated alkylphenols, polyoxyethylenated oleyl or stearylamines, alkyl or alkylphenyl sulfonates and dispersants, e.g. lignosulfonic acid sodium, 2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium, dibutylnaphthalenesulfonic acid sodium or oleylmethyltaurine acid. Emulsifiable concentrates are prepared by dissolving the active ingredient in an organic solvent, e.g. Butanol, cyclohexanone, xylene or higher-boiling aromatics.

In order to achieve good suspensions or emulsions in water, wetting agents from the above-mentioned series are also added.

For herbicidal agents, the concentrations of the active ingredients in the commercial formulations may be different. In wettable powders, the drug concentration ζ varies. B. between about 10% and 80%, the remainder consists of the above-mentioned formulation additives. For emulsifiable concentrates, the drug concentration is about 10% to 60%. For use, the commercial concentrates are optionally diluted in usual, e.g. for wettable powders and emulsifiable concentrates by means of water. Sprayable solutions are no longer diluted with other inert substances before use. With the external conditions such as temperature, humidity and the like. the required application rate varies. It can vary widely, e.g. between 0.1 kg / ha and 10 kg / ha of active substance, but is preferably between 0.3 and 3 kg / ha.

embodiment

The following examples serve to further illustrate the invention: A. Chemical Examples

example 1

N-DL-phosphinothricyl DL Ieucinmethylester

23.6 g (0.075 mol) of Cbo-DL-phosphinothricin and 15.0 g (0.0825 mol) of DL-leucine methyl ester hydrochloride are dissolved with 7.6 g (0.075 mol) of triethylamine in 150 ml of tetrahydrofuran. At 0 ⁰ C is added dropwise to a solution of 19.5 g (0,09mol) of dicyclohexylcarbodiimide in 30 ml of tetrahydrofuran. The mixture is stirred for 15 hours at 0 ⁰ C, decomposes excess dicyclohexylcarbodiimide with 2 ml of glacial acetic acid, the precipitated solid is filtered off and the filtrate concentrated in vacuo. The residue is taken up in ethyl acetate and washed with 0.5 N hydrochloric acid and water. After drying the organic phase with Na ₂ SO 4 and concentration in vacuo left behind 29.9 g of crude N-Cbo-DL-phosphinothricyl-DL-leucine methyl ester. Is cleaved, the Cbo-protecting group by dissolving in 200 ml of methanol, adding 4.5 ml glacial acetic acid and 3 g of palladium on charcoal (10%) and introducing a H ₂ stream in the ⁰ to 40 C heated solution until no CO ₂ - Development is observed more. The catalyst is filtered off and evaporated in vacuo. Trituration of the residue with acetone, suction filtration and drying gives 15.0 g (yield of the two stages 66%) of N-DL-phosphinothricyl-DL-Ieucinmethylester of mp. 153-155 ⁰ C.

Example 2

N-DL-phosphinothricyl-DL-leucine

10.0 g (0.032 mol) of N-DL-phosphinothricyl-DL-leucine methyl ester are concentrated in 60 ml. Hydrochloric acid for 2 hours at 50 ⁰ C heated.

It is evaporated to dryness in vacuo and the residue is dissolved in 100 ml of absolute ethanol. After addition of 10 ml of propylene oxide is stirred for 5 hours at room temperature, filtered off and dried. This gives 6.5 g (69%) N-DL-DL-leucine phosphinothricyl-mp. 206 ⁰ C.

Example 3

N-DL-phosphinothricyl-L-phenylalanyl-DL-alanine hydrochloride

7.0 g (0.017 mol) of N-DL-phosphinothricyl-L-phenylalanyl-DL-alanine methyl ester are concentrated in 80 ml. Hydrochloric acid heated to 40 ° C for 2 hours. It is evaporated in vacuo, dried and replaced with 6.6 g (89%) of N-DL-phosphinothricyl-L-phenylalanyl-DL-alanine hydrochloride of mp. 154-155 ⁰ C (dec.).

The following compounds of general formula I listed in Table 1 can be obtained in an analogous manner.

TABLE 1*

Η-amino acid! - (amino acid !!! "- amino acid I

I-OR · (HX) _n

Bsp.- amino amino amino R X m η Mp CC) No. acid I acid II acid III 4 L-Ptc Gly CH ₃ - 0 0 5 L-Ptc - Gly H Cl I 0 6 L-Ptc - Gly N / A - 0 0 7 DL-Ptc - Gly CH ₃ - 0 0 255-260 Z. a DL-Ptc - Gly H Cl I 0 9 L-Ptc - L-Ala CH ₃ - 0 0 ro L-Rc - L-Ala H Cl I 0 11 L-Ptc - DL-Ala CH ₃ 0 0 12 L-Ptc - DL-Ala H Cl I 0 13 DL-Ptc - L-Ala CH ₃ - 0 0 14 DL-Ptc - L-Ala H Cl I 0 15 DL-Ptc - DL-Ala H Cl I 0 16 L-Ptc - / 3-Ala H - 0 0 17 DL-Ptc , - / 3-Ala H Cl I 0 Glass 18 DL-Ptc - / 3-Ala H - 0 0 T9 L-Ptc - L-Val H - 0 0 20 L-Ptc - DL-Val H - 0 0 21 DL-Ptc - L-Val H - 0 0 22 DL-Ptc - DL-Val H - 0 0 218 23 DL-Ptc - DL-Val CH ₃ - 0 0 165-166 24 L-Ptc - L-Leu H - 0 0 25 L-Ptc - DL-Leu H - 0 0 26 DL-Rc - L-Leu H - 0 0 27 DL-Ptc - DL-Leu H Cl I 0 28 DL-Ptc - L-Leu CH ₃ - 0 0 29 L-Rc - L-IIe H - 0 0 30 L-Rc - DL-IIe H 0 0 31 DL-Rc - L-IIe H - 0 0 217 32 DL-Ptc - DL-IIe H - 0 0 33 L-Rc - L-Phg H - 0 0 34 L-Rc - DL-Phg H - 0 0 35 DL-Rc - L-Phg H - 0 0 36 DL-Rc - DL-Phg H - 0 0 120Zers. 37 DL-Ptc - DL-Phg CH ₃ - 0 0 182-184 Z. 38 D-Rc - L-Phe H - 0 0 39 L-Rc - DL-Phe H - 0 0 40 DL-Rc - L-Phe H - 0 0 215-219 Z. 41 DL-Rc - DL-Phe H - 0 0 Glass 42 DL-Rc - L-Phe CH ₃ 0 0 210 43 DL-Ptc - DL-Phe CH ₃ Cl 1 0 148-150 Z. 44 DL-Rc - D-Phe CH ₃ Cl 1 0 120-123 Z. 45 DL-Ptc - D-Phe H Cl 1 0 135 Z. 46 L-Ptc - L-Ser H - 0 0 47 L-Rc - DL-Ser H. 0 0 48 DL-Ptc - L-Ser H - 0 0 49 DL-Ptc - DL-Ser H - 0 0 50 L-Rc - L-Thr H - 0 0 51 L-Rc - DL-Thr H - 0 0 52 DL-Ptc - L-Thr H - 0 0 53 DL-Ptc - DL-Thr H - 0 0 54 L-Rc - L-Met H - 0 0 55 L-Rc - DL-Met H - 0 0 56 DL-Ptc - L-Met H - 0 0 57 DL-Rc - DL-Met H - 0 0 58 L-Rc - L-Tyr H - 0 0 59 L-Rc - DL-Tyr H ' - 0 0 60 DL-Rc - L-Tyr H - 0 0 61 DL-Rc - DL-Tyr H - 0 0 62 L-Rc L-Glu H 0 0

Ex. · No.

Amino acid I

Amino Acids Amino Acid III

Fp- ( ⁰ C)

63 L-Ptc - 64 DL-Ptc - ' 65 DL-Ptc - 66 L-Ptc - 67 L-Ptc - 68 DL-Ptc - 69 DL-Ptc - 70 L-Ptc - 71 L-Ptc 72 DL-Ptc - 73 DL-Ptc 74 L-Ptc - 75 L-Ptc - 76 DL-Ptc 77 DL-Ptc - 78 L-Ptc 79 L-Ptc 80 DL-Ptc - 81 DL-Ptc 82 L-Ptc 83 L-Ptc - 84 DL-Ptc 85 DL-Ptc 86 L-Ptc - 87 L-Ptc 88 DL-Ptc 89 DL-Ptc - 90 L-Ptc - 91 L-Ptc 92 DL-Ptc 93 DL-Ptc - 94 L-Ptc 95 L-Ptc 96 DL-Ptc 97 DL-Ptc 98 L-Ptc 99 DL-Ptc 100 DL-Ptc 101 L-Ptc 102 DL-Ptc 103 L-Ptc 104 DL-Ptc - 105 L-Ptc 106 DL-Ptc 107 L-Ptc 108 DL-Ptc - 109 L-Ptc 110 DL-Ptc 111 DL-Ptc Gly 112 L-Ptc Gly 113 DL-Ptc Gly 114 L-Ptc Gly 115 DL-Ptc Gly 116 L-Ptc Gly 117 DL-Ptc Gly 118 L-Ptc Gly 119 DL-Ptc Gly 120 L-Ptc Gly 121 DL-Ptc Gly 122 L-Ptc Gly 123 DL-Ptc Gly 124 L-Ptc Gly 125 DL-Ptc Gly 126 L-Ptc Gly 127 DL-Ptc Gly

DL-Glu H - 0 0 145-147Z L-Glu H - o 0 DL-Glu H - 0 0 L-Gln H - '0 0 DL-Gln H - 0 0 L-Gln H - 0 0 DL-Gln H - 0 0 L-As ρ H - 0 0 DL-Asp H - 0 0 L-As ρ H - 0 0 DL-Asp H - 0 O L-As η H - 0 0 DL-Asn H - 0 0 L-Asn H - 0 0 DL-Asn H - 0 0 L-Lys H - 0 0 DL-Lys H - 0 0 L-Lys H - 0 0 187-190Z DL-Lys H - 0 0 L-Nle H - 0 0 DL-Nle H - 0 0 L-Nle H -. 0 Ö DL-Nle H - o 0 L-Nva H - 0 0 DL-Nva H - 0 0 L-Nva H - 0 0 DL-Nva H - 0 0 260Zers. L-Cys H - 0 0 DL-Cys H - 0 0 L-Cys H - 0 0 DL-Cys H - 0 0 L-Abu H - 0 0 DL Abu H - 0 0 L-Abu H - 0 0 DL Abu H - 0 0 y-Abu H - 0 0 -y Abu H - 0 0 y-Abu CH ₃ - 0 0 238 DL-Phg (4CI) H - 0 0 DL-Phg (4CI) H - 0 0 DL-Phg (2CI4Cf ₃₎ H - 0 0 DL-Phg (2CI4Cf ₃₎ H - 0 0 DL-Phe (4CI) H - 0 0 DL-Phe (4CI) H - 0 0 DL-Phe (4NO ₂ ) H - 0 D DL-Phe (4NO ₂ ) H - 0 0 DL-VaI (aMe) H - 0 0 DL-VaI (aMe) H - 0 0 DL-Ala CH ₃ - 0 / 3-Ala H - 0 0-Ala H - 0 L-Leu H - 0 DL-Leu H - 0 L-IIe H - 0 L-IIe H - 0 L-Phg H - 0 DL-Phg H - 0 L-Phe H - 0 DL-Phe H -_ Π L-Met H - 0 DL-Met H - 0 L-Nle H - 0 DL-Nle H - 0 L-Nva H -. ο DL-Nva H - 0

Ex. amino amino amino R X m ι Fp. ("C) No. acid I acids acid IM 128 DL-Ptc DL-Ala DL-Val CH ₃ - 0 l 186-188 Z. 129 L-Ptc L-Ala DL-Leu CH ₃ - 0 l 130 DL-Ptc DL-Ala DL-Leu C ₂ H ₅ - 0 l 131 · L-Ptc. L-Ala L-IIe H - 0 l 132 DL-Ptc DL-Ala DL-IIe J-I - 0 l 133 L-Ptc L-Ala L-Phg H - 0 134 DL-Ptc DL-Ala DL-Phg H - 0 135 DL-Ptc L-Ala DL-Phg CH ₃ - 0 142-145 Z. 136 DL-Ptc DL-Ala DL-Phg H Cl 0 115-118Z. 137 L-Ptc L-Ala L-Phe H - 0 138 DL-Ptc DL-AIa " DL-Phe H - 0 139 DL-Ptc DL-Ala L-Phe CH ₃ - 0 131-134 Z. 140 DL-Ptc DL-Ala L-Phe H Cl I 148-151 Z. 141 L-Ptc L-Ala L-Met H - 0 142 DL-Ptc DL-Ala DL-Met H - 0 143 L-Ptc L-Ala L-Nle LJ _- _ 0 144 DL-Ptc DL-Ala DL-Nle H - 0 · · 145 L-Ptc L-Ala J ^ -Nva H - 0 146 DL-Ptc DL-Ala DL-Nva 0 147 DL-Ptc DL-Ala -y Abu H - 0 148 L-Ptc L-Ala L-Th r H - 0 149 L-Ptc L-Ala L-Tyr H - 0 150 L-Ptc L-Ala L-Glu H - 0 151 L-Ptc 'L-Äla L-Gln H - 0 152 L-Ptc L-Ala L-Asp H - 0 153 L-Ptc L-Ala L-As η H - 0 154 L-Ptc L-Ala L-Lys H - 0 155 L-Ptc L-Ala L-Cys H - 0 156 DL-Ptc DL-Ala DL-Phg (4Cl) H - 0 157 DL-Ptc DL-Ala DL-Phe (4Cl) H - 0 158 DL-Ptc DL-Ala DL-VaI (aMe) H - 0 159 DL-Ptc DL-Ala AIa (aMe) LJ 0 160 L-Ptc / 3-Ala y S-Ala H - 0 161 L-Ptc / 3-Ala L-Val H - 0 162 L-Ptc 0-Ala L-Abu H - 0 163 L-Ptc (3-Ala L-Phg LJ __ 0 164 L-Ptc / 3-Ala L-Phe H - 0 165 L-Ptc , / 3-Ala L-Leu H - 0 166 L-Ptc L-Val / 3-Ala H - 0 167 L-Ptc L-Val L-Phg H - 0 168 L-Ptc L-Val L-Phe H - 0 169 L-Ptc L-Val L-Leu H - 0 170 L-Ptc L-Abu / 3-Ala H - 0 171 L-Ptc L-Abu L-Phg H - 0 172 L-Ptc L-Abu L-Phe H - 0 173 L-Ptc L-Abu L-Leu H - 0 174 L-Ptc L-Phg / 3-Ala Lj _- _ 0 175 L-Ptc L-Phg L-Val H - 0 176 L-Ptc L-Phg L-Abu H - 0 177 L-Ptc L-Phg L-Phg H - 0 178 L-Ptc L-Phg L-Phe H - 0 179 L-Ptc L-Phg L-Leu LJ " 0 180 L-Ptc L-Phe / 3-Ala H - 0 181 L-Ptc L-Phe L-Val LJ __ 0 182 L-Ptc L-Phe L-Abu H - 0 183 L-Ptc L-Phe L-Phg H - 0 184 L-Ptc L-Phe L-Phe LJ ___ 0 185 L-Ptc L-Phe L-Leu H - 0 186 L-Ptc L-Leu ß-A \ a H - 0 187 L-Ptc L-Leu L-Val H - 0 188 L-Ptc L-Leu L-Abu H - 0 189 L-Ptc L-Leu L-Phg H - 0 190 L-Ptc L-Leu L-Phe H - 0 191 L-Ptc L-Leu L-Leu H - 0 192 L-Ptc / 3-Ala Gly H - 0 193 DL-Ptc / 3-Ala Gly H - 0

Bsp.- amino amino amino R X m ι Fp. (X) - 171-174Z. No. acid I acids acid III 194 L-Ptc L-Val Gly H 0 195 DL-Ptc DL-Val Gly H - 0 196 L-Ptc L-Leu Gly H. - 0 197 DL-Ptc DL-Leu Gly H - 0 198 L-Ptc L-IIe Gly H - 0 199 DL-Ptc L-IIe Gly H - 0 200 L-Ptc L-Phg Gly H - 0 201 DL-Ptc. DL-Phg Gly H - 0 202 L-Ptc L-Phe Gly H - 0 203 DL-Ptc DL-Phe Gly H - 0 204 L-Ptc L-Met Gly H - 0 205 DL-Ptc DL-Met Gly H - 0 206 L-Ptc L-Nle Gly H - 0 207 DL-Ptc DL-Nle Gly H - 0 208 L-Ptc L-Nva Gly H - 0 209 DL-Ptc DL-Nva Gly H - 0 210 L-Ptc / 3-Ala L-Ala H - 0 211 DL-Ptc 0-Ala DL-Ala H - 0 212 DL-Ptc DL-Val DL-Ala CH ₃ - 0 Glass 213 L-Ptc L-IIe L-Ala H - 0 214 DL-Ptc DL-IIe DL-Ala H - 0 215 L-Ptc L-Leu L-Ala H - 0 216 DL-Ptc DL-Leu DL-Ala H - 0 217 L-Ptc L-Phg L-Ala H - 0 218 DL-Ptc DL-Phg DL-Ala H - 0 219 DL-Ptc DL-Phg DL-Ala CH ₃ - 0 169-172 Z. 220 DL-Ptc DL-Phg DL-Ala H Cl I 155-158 Z. 221 L-Ptc L-Phe L-Ala H - 0 222 DL-Ptc DL-Phe DL-Ala H - 0 223 DL-Ptc L-Phe DL-Ala CH ₃ - 0 224 DL-Ptc DL-Phe DL-Ala H Cl I 225 L-Ptc L-Met L-Ala H - 0 226 DL-Ptc DL-Met DL-Ala H - 0 227 L-Ptc L-Nle L-Ala H 0 228 DL-Ptc DL-Nle DL-Ala H - 0 229 L-Ptc L-Nva L-Ala H - 0 230 DL-Ptc DL-Nva DL-Ala H - 0 231 DL-Ptc y-Abu DL-Ala H - 0 232 L-Rc L-Thr L-Ala H - 0 233 L-Ptc L-Tyr L-Ala H - 0 234 L-Ptc L-Glu L-Ala H - 0 235 L-Ptc L-Gln L-Ala H - 0 236 L-Ptc L-Asp L-Ala H - 0 237 L-Ptc L-Asn L-Ala H - 0 238 L-Ptc L-Lys L-Ala H - 0 239 L-Ptc L-Cys L-Ala H - 0 240 DL-Ptc DL-Phg (4Cl) DL-Ala H .- 0 241 DL-Ptc DL-Phe (4 Cl) DL-Ala H - 0 242 DL-Ptc DL-VaI (aMe) DL-Ala H 0 243 DL PTc AIa (aMe) DL-Ala H 0 244 DL-Ptc AIa (aMe) L-Ala H - 0

* The individual amino acids are designated by abbreviations, which are generally used in peptide chemistry (Houben-Weyl, Vol. 15/1, p.2ff). Phosphinothricin is abbreviated "Ptc".

In capital letters before the respective amino acid, the stereochemistry of the existing centers of asymmetry is given. Z = decomposition point.

B. FORMULATION EXAMPLES Example 1

A 20% aqueous solution is obtained from: 20% by weight of active compound 10% by weight of nonylphenol 10AeO 20% by weight of ethylene glycol 50% by weight of water.

Example 2

A wettable powder readily dispersible in water is obtained by adding 25% by weight of active ingredient

64% by weight of kaolin-containing quartz as inert material

10% by weight of lignosulfonic acid potassium and

Mix 1% by weight of oleylmethyltaurine sodium as wetting and dispersing agent and mill in a pin mill.

C. BIOLOGICAL EXAMPLES

Damage to weed plants or crop plant compatibility was rated according to a key in which the efficacy is expressed by values of 0-5. Where:

0 = no effect or damage

1 = 0-20% effect or damage

2 = 20-40% effect or damage

3 = 40-60% effect or damage

4 = 60-80% effect or damage

, 5 = 80-100% effect or damage

T. weed effect postemergence

Seeds or rhizome pieces of monocotyledonous and dicotyledonous weeds were placed in sandy loam soil in plastic pots (0 = 9 cm), covered with soil and grown in the greenhouse under good growth conditions. Three weeks after sowing, the test plants were treated at the trefoil stage.

The compounds according to the invention formulated as wettable powders, as emulsion concentrates or as aqueous solutions were sprayed onto the green plant parts in various dosages with a water application rate of 600 l / ha and after approx. 3-4 weeks life of the test plants in the greenhouse under optimal growth conditions (Temperature 23 plus / minus 1 ⁰ C, relative humidity 60-80%) the effect of the preparations optically scored compared to untreated controls. The compositions according to the invention have postemergence good herbicidal activity against a broad spectrum of economically important weeds and weeds.

Table 2

Herbicidal action of the compounds of the invention. post-emergence

product dose AVF SAL herbicidal action SIA CRS STM Expl kga. a.i./ha 3 5 ECG 5 5 5 23 2.4 1 4 4 4 5 4 0.6 1 5 3 3 3 3 1 2.4 1 3 3 5 5 4 0.6 4 5 1 5 5 5 7 2.4 2 5 5 5 5 5 0.6 5 5 5 5 5 5 42 2.4 3 5 5 5 5 4 0.6 4 • 5 5 5 5 5 22 2.4 1 3 5 3 ' 5 3 0.6 3 5 2 5 5 5 100 ' 2.4 2 4 5 5 5 4 0.6 2 4 3 5 5 5 3T 2.4 1 2 5 4 5 5 0.6 3 5 2 5 5 5 2 2.4 2 4 5 5 5 4 0.6 4 5 3 5 5 5 37 2.4 2 5 5 5 5 5 0.6 5 5 4 5 5 5 40 2.4 4 5 5 5 5 5 0.6 4 5 5 5 5 5 89 2.4 1 5 5 4 5 4 0.6 3 5 4 4 4 4 80 2.4 1 4 4 1 2 3 0.6 - - 1 5 5 5 36 2.4 - - 5 - - - 0.6 - - - 5 5 5 17 2.4 - - 5 - - - 0.6 - - - 5 5 5 128 2.4 - 5 - - - 0.6 -

Abbreviations:

AVF = Aventa fatua (flying oats)

SAL = Setaria lutescens (bristle-millet)

ECG = Echinochloa crus-galli (chicken millet)

SIA = Sinapisalba (white mustard)

CRS = chrysanthemum segetum (seedwort flower)

Claims (4)

1. agent for weed control, characterized by a content of compounds of the forms! I ^ 0 · / R ³ _N R ^{5 H} 3 ^G v H / I \ I Λ > Np_CH ₂ -GH ₂ -GH-GO (LiH-G- (GH ₂ ) -GO] IM-C- (CH ₂ ) -COOR ¹ (|) ^m 2 'R ^{2 R} R ^{1 is} hydrogen or (C ₁ -C ₁₂ ) -alkyl, R ² and R ⁴ independently of one another are hydrogen, (C ₁ -C ₁₂ ) -alkyl, (C ₃ -C ₈ ) -cycloalkyl, phenyl or phenyl (C 1 -C 4) -alkyl, where the groups mentioned are in turn denoted by halogen, NH ₂ , OH, SH, NO ₂ , CF ₃ , (C ₁ -C ₄ -alkoxy, (C ₁ -C ₄ -alkyl), (C ₁ -C ₄ -alkoxycarbonyl, COOH or CONH ₂ may be substituted, R ³ and R ^{5 are} hydrogen or methyl, η O or 1, and ο and ρ are independently 0, 1, 2, 2 or 3 except for compounds in which a) η = O, R ⁴ = H or CH ₃ and R ⁵ = H; or b) η = 1, R ³ and R ⁵ = H, and R ² and R ^{4 are} H, CH ₃ , C ₂ H ₅ , CH (CH ₃ J ₂ or CH ₂ OH; c) η = 1, R ³ and R ⁵ = H, R ² = CH ₃ and R ⁴ = CH ₂ CH (CH ₃ J ₂ , and their salts with bases or acids, in addition to customary auxiliaries and carriers. 2. Composition according to claim 1, characterized in that in the compounds of formula IR ¹ hydrogen or (C ₁ -C ₈ J-AIkYl, R ² and R ⁴ are each independently H, (C ₁ -C ₄ ) alkyl, (C ₃ -C ₄₎ AmJnOaIkYl, hydroxymethyl, hydroxyethyl, thiomethyl, methylthioethyl, carboxymethyl or ethyl, carbamoylmethyl or -ethyl, carbo _(Cr-C4) alkoxymethyl or -ethyl, phenyl, benzyl or hydroxybenzyl, R ³ and R ^{5 are} H or CH ₃ , η 0 or 1, and ο and ρ independently of one another denote O, 1 or 2, excluding the compounds listed above under a), b) and c) and salts thereof. 3. Use of compounds of the formula I according to claims 1 or 2, characterized in that they are used for controlling unwanted plant growth. 4. A method for controlling undesired plant growth, characterized in that applying an effective amount of a compound of formula I according to claims 1 or 2 to the plants to be controlled or the area to be treated in the pre-seed, pre-emergence or post-emergence.