DD224203A1 - POLYMER PHYTOEFFECTORS AS NEW MEANS FOR BIOLOGICAL PROCESS CONTROL - Google Patents

Abstract

The invention relates to the use of 3-amino-1,2,4-triazole chemically bound to a Polymerrueckgrat as Phytoeffektor with primarily herbicidal activity and improved stability against physical, chemical and biochemical degradation processes in both leaf and soil applications. The novel polymer-bound 3-amino-1,2,4-triazoles can be used alone or in combination with other low molecular weight or polymer-bound active compounds, depending on the intended use.

Description

Title of the Invention Polymer bound 3-amino-1,2,4-triazole as a new phyto-effector

Field of application of the invention

The invention relates to the use of chemically bound to a polymer backbone 3-amino-1,2,4-triazole as Phytoeffektor with primarily herbicidal activity.

Growth-regulating substances with high water solubility have the disadvantage that they are washed off relatively quickly by rainfall or artificial irrigation both directly from the plant as well as evade by washing out and draining into deeper soil layers of a root intake. The 3-amino-1,2,4-triazole is a foliar herbicide with systemic action. It gets swiftly from the leaves, but also through the. Taken roots. Due to its high solubility in water, however, it comes to significant drug losses on the leaf surfaces. Furthermore, a rapid decline in the concentration of active substance due to washout and fast metabolization processes is also recorded in the soil. Increasing the persistence of the 3-amino-1,2,4-triazole on both the plant and upper root-near soil layers would result in greater drug efficacy. The possible reduction of the previous application rates as well as an extended duration of action is associated with considerable benefit.

Characteristic of the known technical solutions

It is known that 3-amino-1,2,4-triazole has growth-regulating properties and is used as a herbicide (US Pat. No. 2,670,282).

The efficiency of this substance is due to its low molecular weight nature and high water solubility of physical, chemical and biological processes, such. B. leaching, degradation to less active or inactive metabolites, essential'influences. A lateral, reversible, chemical fixation by covalent bonding of 3-amino-1,2,4-triazole to polymer chains to influence its biological efficiency has not been described. In the US Patent 2,824,086 the incorporation of 3-amino-1,2,4-triazole in polymer chains by reaction with organic diisocyanates and carbonic acid esters is reported, resulting in polymers having softening points above 300 ⁰ C, which are thermoplastic and due their good heat resistance for use as materials. Side-bound to a polymer chain 3-amino-1,2,4-triazole is described by GG Skworzova et al. [Khim. Geterosikl. Soed. J_1_, 1566 (1973)] by radical polymerization of N-vinyl-3-amino-1,2,4-triazole. In these publications, however, there are neither statements about a release of the polymer-bound 3-amino-1,2,4-triazole nor about biological effects.

Furthermore, it is known from the patent literature that physical mixtures of polymeric substances and 3-amino-1,2,4-triazole, such as polystyrene-based granules, masses of butene-1 polymer or other polymeric plastics can be prepared to control a controlled release , However, this physical embedding of the active ingredient in a polymer matrix has hitherto brought no significant advantages over the "solo use" of amitrole due to the only labile adhesion of 3-amino-1,2,4-triazole to the support materials used.

The release of active substance and its correlation to the total duration of action are still unsatisfactory, so that practical uses have not been known so far.

Object of the invention

The aim of the invention is to overcome the disadvantages of the 3-amino-1,2,4-triazole known as phyto-effector, as well as its physical mixtures with polymers, by the development of new, covalently polymer-bound phyto-effectors with 3-amino-1,2,4-triazole. to reduce triazole as an active component with significantly improved stability to physical, chemical and biochemical degradation processes.

Explanation of the essence of the invention

The object of extensive protection against the aforementioned degradation processes is inventively achieved by the biologically active 3-amino-1,2,4-triazole is reversibly chemically bonded via both the heterocyclic nitrogen and the exo-containing amino group amide-like to a polymer backbone. This results in predominantly water-insoluble drug reservoirs from which 3-amino-1,2,4-triazole can be released controlled by hydrolysis or by the influence of microorganisms / It has been found that polymer-bound 3-amino-1,2,4- triazole of the general formula I, II and III

Il

II

on

M-

ΎΥΙ

NH

III

herbicidally effective, as the corresponding low molecular weight acyl derivatives of 3-amino-1, 2, '4-triazole, but it is much more stable to hydrolysis.

In formulas I, II and III, R is an organic radical which is part of a polymer chain. ··.

M-

IV

c -η ^m

C- O

C = O

The compounds according to the invention with 3-amino-1,2,4-triazole polymer-bound via different amide groups can contain, in addition to the two basic building blocks of the general formulas IV and V, further building blocks R 'which are selected from a vinyl comonomer, such as, for example, US Pat. As styrene, methyl methacrylate, acrylic acid, p-vinyldiphenyl, vinyl acetate, among others, have emerged. R-GO- represents a polymerized acyl radical, the z. B. from acrylic acid, methacrylic acid, 4-vinylbenzoic acid, allylacetic acid, the Fumarsäuremonoethylester or another unsaturated acid may have been formed. By suitable selection of R and R, it becomes possible to make the hydrophilic or hydrophobic properties of the biocidal polymers variable and to adjust them according to the application-related requirements. Both by altering the neighboring group interaction as well as by additional crosslinking reactions, the cleavage of the biologically active 3-amino-1,2,4-triazole from the polymers is modifiable. The polymeric compounds of the invention I, II _{un (j} Uj _{WUR (} en} preferably prepared by free radical polymerization or copolymerization of unsaturated acyl derivatives of 3-amino-1,2,4-triazole.

The suitable for homo- or copolymerization, unsaturated 1-acyl-5-amino-i, · 2,4-triazoles are prepared by known synthetic methods from the corresponding unsaturated carboxylic acid chlorides and 3-amino-1,2,4-triazole in THF at 0 - 20 ⁰ C produced. For the synthesis of the isomeric 3-acylamino-1,2,4-triazoles, the reaction of the unsaturated carboxylic acid chlorides with '1-acetyl-5-amino-i, 2,4-triazole, which is a hydrolysis of the corresponding N, N' Diacyl compound connects. The 3-allylacetylamino-1,2,4-triazole is obtainable with significantly increased yield by thermal rearrangement of the 1-allylacetyl-5-amino-1,2,4-triazole. Examples of the unsaturated acyl-3-amino-1,2,4-triazoles used in the context of the invention are listed in Tables 1 and 2 [h. Bauer, M. Hartmann, K. Wermann; Makromol. Chem. 183 , 2971 (1982); M. Hartmann, K. Wermann; Z. Chem. _23, 97 (1983)].

The unsaturated starting materials are converted by known methods in solution (preferably in DMP or DMSO) or in substance preferably by free-radical polymerization into the compounds I, II and III according to the invention, their polymerization and copolymerization behavior corresponding to the structurally similar unsaturated acyl derivatives. In Tables 3, 4 and 5, a selection of hitherto unknown compounds I, II and III according to the invention is shown.

The advantage of these compounds I, II and III compared to 3-amino-1,2,4-triazole and low molecular weight acyl-3-amino-1,2,4-triazoles consists in the substantial water insolubility and a relatively increased resistance to hydrolysis. They have in part film-forming properties and are much more difficult to wash out. Furthermore, it is advantageous that the complete or partial release of the biologically active 3-amino-1,2,4-triazole by controllable chemical and physical factors such as binding to the polymer backbone, variation of the polymer backbone taking into account steric and electronic effects, hydrophilicity / hydrophobicity of the polymer matrix and incorporation of crosslinking sites in accordance with the application

purpose can be targeted. From these advantages it becomes apparent that the conditions for a more effective use of, for example, the herbicidal action of 3-amino-1,2,4-triazole are given.

The application of the compounds I, II and III according to the invention is advantageously carried out together with suitable carriers and / or diluents and u. U. surface-active substances or other conventional excipients in the form of dusts produced by conventional methods, wettable powders, granules, pastes, etc. by dusting, spraying, scattering or pouring. Depending on the intended use, the polymer-bound 3-amino-1,2,4-triazoles can be used alone or in combination with other low molecular weight or polymer-bound active compounds.

The following examples illustrate the invention without limiting it.

Exemplary embodiments Example 1

The compounds of the invention are hydrolyzed in a thermostated vessel with bidistilled water with stirring (particle size of the polymers 0.063 mm to 0.2 mm). At certain intervals 5 ml samples are removed via a frit and the hydrolysis volume is completed again with 5 ml bidistilled water. The released active ingredient 3-amino-1,2,4-triazole contained in the samples taken is quantitatively determined directly in aqueous solution by UV spectroscopy with evaluation of the absorption maximum at 198-200 nm (detection limit 3-15 ppm) (see Table 6). ,

Example 2

In pot experiments, using a bottom of medium sorption capacity (SL) at a water capacity of 60%, the herbicidal activity o. Tested substances in pre- and post-emergence treatment. The application of the new chemical compounds was carried out as a wettable powder in aqueous suspension by injector syringe immediately after sowing the weeds (VA) and 14 days growing stocks (NA). The following key was used to assess the herbicidal potency:

Boniturnote Damage weed stock

1 2 3

5 6 7 8 9

Representative of the compounds according to the invention, the test results are shown in Table 7a-c using the specified rating scale.

The results of the compounds listed in Table 7a were obtained under standardized experimental conditions, while the examples listed in Table 7b were tested under extreme experimental conditions, increased irrigation at higher temperatures. Under these conditions, the high water solubility and the metabolism of amitrole, which lead to significant drug losses, particularly evident.

destroyed 0 5 30 50 70 85 95 unharmed 100

The cited examples, however, show greater drug efficacy and a longer duration of action, as can be seen from Table 7c. In this experiment, a re-sowing of test plants took place 4 weeks after the application of the first test plants.

Table 1: Unsaturated 1-acyl-5-amino-1,2,4-triazoles

N CO

NH,

Ser. No, CHp = R 1 CH ₂ = CH 2 CH ₂ = C (CH ₃ ) 3 4-CH ₂ CH- (CH ₂ ) ₂ 4 E-CH ₃ - GH-C ₆ H ₄ 5 OOC-CH = CH

• ( ⁰ C)

171 113 114 160 176

Table 2: Unsaturated 5-acylamino-1,2,4-triazoles

h-NH-CO

HN-f

Ser. No.

Mp ( ⁰ C)

CH ₂ = CH CH ₂ = C (CH ₃ ) CH ₀ = CH- (CH ₀ ),

4-CH ₂ = CH-C ₆ H ₄ E-CH ₃ OOG-CH = CH 295 216 214 276 260

Table 3: Polymers 1-Acyl-5-amino-i, 2,4-triazoles

^ M

Ser.

Coronomer for R ¹

Amitrole content (weight JJ)

M .10 (g / mol)

15 16 17 18 19 20 21 22 23

-CH ₂ -CH-

-CH ₂ -CH-

-CH ₂ -CH-

-CH ₂ -GH-

-CH ₂ -C (CH ₃ ) -

-CH ₂ -C (CH ₃ ) -

-CH ₂ -C (CH ₃ ) -

-CH ₂ -CH-C ₆ H ₄ -

-CH ₂ -CH-C ₆ H ₄ -

-CH ₂ -CH-C ₅ H ₄ -

I -CH ₂ -CH-C ₆ H ₄ -

i -CHp-CH-C / -Hl · -

-CH ₂ -CH-C ₆ H ₄ -

-CH ₂ -CH-C ₅ H ₄ -

styrene

methyl methacrylate

acrylic acid

Styrene methylmethacrylate

styrene

Methyl methacrylate vinyl acetate acrylic acid

1-acryloyl-5-amino-1,2,4-triazole

1-methacryloyl-5-amino-1,2,4-triazole

CH ₃ OOC-CH-CH-

styrene

p-vinyldiphenyl-CH ₀ -CH- (CH ₀ ) _o - vinyl acetate

CH ₃ OOC-CH-CH-

59.6 6.3 13.0 24.4 54.0 28.0 28.5 36.8 27.1 22.9 26.1 25.4 28.0

32.2

26.0 21, 1 5,7

a)

6.1

5.1

100.0

5.0

7.5

2.3 3.8 2.4 3.3

2.2

·,

prepared by polymer-analogous reaction of activated by Chlorameisensäureethvlester polyacrylic acid with amitrole

Table 4: Polymers 3-Acylamin.o-1, 2, 4-triazoles

HM-

NH

ft;

- <rn.

Ser.

No.

Comonomer for R ¹

amitrole

salary

(Aew.%)

M .10 ^ (g / mol)

28 -CHG-CH-

29 -CH ₂ -CH-

30 -CHG-CH-

31 -CH ₂ -C (CH ₃ ) -32. -Chg-C (CH ₃₎ -

33 -CHg-C (CH ₃ ) -

34 -CHg-CH-C ₆ H ^ -

35 -CHG-CH-C ₍

36 -CHg-CH-C ₆ H ^ -

I i

37 CH ₃ OOC-CH-CH-

38 GH-OOC-CH-CH-

I i

39 CH ₃ OOC-CH-CH-

40 -CHg-CH- (CHg) -

Styrene methylmethacrylate

Styrene methylmethacrylate

styrene

methyl methacrylate

styrene

p-Vinyldiphenyl

vinyl acetate

vinyl acetate

59.5 22.4 18.5 54.1 18.7 14.3 28.2 (34.6) 25.7 23.2 16.0 28.0 3.1

5.5

1.5

5.7

Table 5:

Copolymers of 1-acyl-5-amino-1,2,4-triazole and '3-acylamino-i, 2,4-triazole

HN N

NH

, III

Ser. No. R R ¹ Amitrole content (% by weight) 41 -CH ₂ -C (CH ₃ ) - I -CH ₂ -CH- 43.4 42 -CH ₂ -C (CH ₃ ) - -CH ₂ -C (CH ₃ ) - 38.0 43 -CHp-C (CHO -CH ₂ -CH-CgH ₄ - 37.6 44 I -CH ₂ -OH-OgH ₄ - I -CHp-CH-CgH ₄ - (22.8) 45 46 I Λπ ΠΧΊ Π XJ -CH ₂ -CH-CgH ₄ - I -CHp-CH-C / -Hr - I / Ίττ ηττ η ττ -OH ₂ -OH-OgH ₄ - -CH ₂ -C (CH ₃ ) - 18,6 22,8

Table 6: Hydrolytic release of polymer-bound 3-amino-i, 2,4-triazole in bidist. HPO

Polymer hydrolysis-released amitrole (%) / Lfd. No. Temperature after hours (tendency) acc. Tab. 3-5 ( ⁰ C)

17 30 18/144 (constant) 60 50/24 (slightly rising) 18   30 38/168 (slightly rising) t ₅₀ = 23 days 60 50/24 (rising, t _10Q = 11 days) 19 30 50/12 (slightly rising) 20 30 50/1 (slightly rising) 21 30 50/168 (slightly rising) 22 30 100/24 25 30 50/24 (rising, t _10Q = 15 days) 60 50/1 (rising, t _10Q = 13 days) 27 30 22/144 (constant) 60 50/60 (strongly rising, Voo ^{= 8 Tase)} 33 30 41/168 (slightly rising) 60 50/120 (slightly rising) 36 30 16/195 (constant) 37 30 20/24 (constant) 60 13/48 (constant) 40 30 100/72

Table 7a:

Standardized experimental conditions according to Example 2

test plants

Application rate 6 kg / ha AS

amitrole

10 kg / ha AS 6 kg / ha AS

Connection No. 14 - 15

VA N / A 3 VA N / A VA N / A 1 Medicago sativa 1 1 (N / A) 1 1 1 1 1 Lactuca sativa 1 1 1 1 1 1 1 1 Lycopersicon esculentum 1 1 1 1 1 1 1 1 Beta vulgaris 1 1 1 1 1 1 1 1 Lolium multiflorum 1 1 1 1 2 1 1 1 Sinapis alba 1 2 1 1 2 1 2 1 Avena sativa 1 1 1 1 1 1 3 1 1 1 1 6 3 kg / ha AS 2 1 Compound 14 (NA 1 Stellaria media 1 1 1 Senecio vulgaris 1 1 1 Anthemis arvensis 1 1 1 Ag'rostemma git hag ο 1 1 1 Lamium purpureum 1 1 Chenopodium album application rate 1 1 Polygonum lapathifolium 6 1 Thlaspi arvense , 1 Spergula arvensis amitrole 1 Galium aparine 1 1 Apera spica-venti 1 1 Poa annua 1 1 Setaria glauca 1 1 Bromus secalinus 1 1 Echinochloa crus-galli 1 1 1 1 1 1 1 1 1 1 1

Table 7b:

Extreme experimental conditions

Greater irrigation / higher temperatures

Application rate.

test plants 6 kg / ha AS amitrole N / A N / A VA Connection No. 20. 27 VA VA N / A VA 3 3 1 , N / A 1 1 1 Medicago sativa 2 2 2 1 i 1 1 1 Lactuca sativa 2 2 2 1 1 1 1 1 Lycopersicon esculentum 2 2 2 3 1 1 2 1 Beta vulgaris 7 4 7 6 2 1 4 2 Lolium multiflorum 6 4 4 3 7 1 1 2 Sinapis alba 3 8th 9 9 5 2 9 6 Avena sativa 7 application rate 9. 3 kg / ha AS amitrole Compound No. 20 27 test plants VA 'VA N / A N / A 2 2 2 1 Medicago sativa 7 2 1 , 1 Lactuca sativa 7 4 2 1 Lycopersicon esculentum 7 9 2 1 Beta vulgaris 9 7 7 4 Lolium multiflorum 6 3 5 4 Sinapis alba 9 9 '9 9 Avena sativa

Table 7c: Reseeding after 4 weeks in the VA

Test plants Amitrol Compound No.

3 6 3 6 kg / ha AS

Lactuca sativa 9 9 7 7

Sinapis alba 9 9 7 5

Avena sativa 9 9 9 8

Claims (1)

invention claim Point 1 Polymeric phyto-effectors as novel biological process control agents, characterized in that they contain polymers of unsaturated 1-acyl-5-amino-1,2,4-triazoles and / or unsaturated 3-acylamino-1,2,4-triazoles of the general formulas I , II and III, wherein R is a polymerized organic radical and R is a comonomer, C = D rrru NH II -.4 _ rn. HH-N. NH C = O III in addition to conventional formulatory agents and / or selected excipients. Point 2 Polymer Phytoeffektoren according to item 1, characterized in that they can be used alone or in combination with the corresponding low molecular weight starting materials. point 3 Polymeric Phytoeffektpren "according to item 1, characterized in that they are applied before or after emergence of the weeds in application rates of 1-10 kg / ha. Point 4 Polymeric Phytoeffektoren according to item 1, characterized in that they can be used in combination with other low molecular weight or polymer-bound Phytoeffektoren.