DD254319B1 - BIOCIDE MEDIUM BASED ON DERIVATIVES OF 2-BROM-2-NITRO-PROPANE-1,3-DIOL - Google Patents

Description

о О Il 2 " С-О -H-O-C

^u (D.

in addition to customary formulation agents, wherein R is a C ₁ - to C ^ alkyl or an optionally substituted phenyl and R ¹ and R ^{2 are} the intermediates of polyfunctional isocyanates or any polyols and may be the same or different, where η is an integer from 1 to 20, in particular from 1 to 10, is.

2. bio-agents according to item 1, characterized in that R ^{1 is} preferably the intermediates of the polyfunctional isocyanates hexamethylene diisocyanate, 4,4-diphenylmethane diisocyanate or 2,4-tolylene diisocyanate or NCO-terminated prepolymers of polyfunctional isocyanates and Oligoethylenglykolen, polyether alcohols or polyester alcohols.

3. Bioeide agent according to item 1, characterized in that R ^{2 is} preferably the members of the polyols oligoethylene glycol, in particular ethylene glycol, diethylene glycol, triethylene glycol and polyethylene glycol (M _n 1000), or polyether alcohols, prepared from ethylene oxide or propylene oxide and glycerol, trimethylolpropane or sugar alcohols , or polyester alcohols from dicarboxylic acids and diols or triols.

4. Bioeide agent according to item 1, characterized in that it mixtures of the oligomers of formula 1 with corresponding diesters of 2-bromo-2-nitro-propane-1,3-diol and optionally 2-bromo-2-nitro-propane Contain 1,3-diol.

5. bio-agents according to item 1 to 4, characterized in that they contain in addition to the usual formulation agents still further organic or inorganic biocides.

Scope of the invention

The invention relates to biocidal agents based on 2-bromo-2-nitro-propane-1,3-diol. This active ingredient and some of the previously known derivatives have a pronounced bactericidal and / or fungicidal action. They are therefore used in many areas of material and storage protection for controlling microorganisms. Typical examples are the use as biocidal ingredients in pharmaceutical and cosmetic preparations as well as bioeids for the treatment of industrial water circuits and for the preservation of feed and other agricultural products. The agents according to the invention are particularly suitable for controlling phytopathogenic microorganisms. They can therefore be used primarily in plant protection under field conditions. Destruction of crop pests involves ensuring high crop yields and considerable economic benefits.

Characteristic of the known technical solutions

The compound 2-bromo-2-nitro-propane-1,3-diol is known to possess bactericidal and fungicidal activities, as described, for example, in US Pat. B. in GB PS 1057131 is described. In GB PS 1193954, reference is made to the bactericidal action of 2-bromo-2-nitro-propane-1,3-diol against Xanthomonas malvacearum and Erwinia amylovora. The control of Erwinia amylovora to Apfelbzw. Pear trees can be done by spraying the orchards. However, the practical use of 2-bromo-2-nitro-propane-1,3-diol is limited due to the very good water solubility of this compound. In particular, when used under field conditions there is the danger after spray application that the active ingredient is washed out by rain and the bactericidal protection is significantly reduced. Further restrictions on the application of 2-bromo-2-nitro-propane-1,3-diol under field conditions arise from its inadequate stability to hydrolysis.

It is also known that certain properties can be altered by the synthesis of derivatives of 2-bromo-2-nitro-propane-1,3-diol. According to DE OS 2847374 and DE OS 2847373 z. B. has been proposed to produce low molecular weight and polymeric esters and urethanes by acylation of both hydroxyl groups of the active ingredient with carboxylic acid derivatives or isocyanates and to obtain in this way, bio-having greater stability and lower toxicity. Of the cyclic derivatives of 2-bromo-2-nitro-propane-1,3-diol, e.g. the 5-bromo-5-nitro-1,3-dioxanes (DEOS 1966920, DE OS 2919466, US Pat. No. 4,025,533), the 5-bromo-5-nitro-2-oxo-1,3,2-dioxa-phosphorinans ( R. VILCEANU, J. NEDA, Phosphorus, Sulfur 8 [1980] 131) and the corresponding chlorophosphinanes (R. VILCEANU, J. NEDA, Rev. Chim. [Bucharest] 31 [1980] 1953),

There is no information from the literature about improved adhesion to plant surfaces and significantly better hydrolysis stability than the starting compounds. 2-bromo-2-nitro-1,3-bis (trimethylsilyloxy) propane has hitherto been of interest only for gas chromatographic studies (DM BRYCE, B. CROSHAW, JE HALL, VR HOLLAND, B. LESSEL, J. Soc., Cosmet 29 [1978] 16).

The acylation of both hydroxyl groups carried out in these derivatives of 2-bromo-2-nitro-propane-1,3-diol leads to a reduction in the water solubility and to an increase in the stability to hydrolysis. At the same time, the biocidal properties of the active ingredients change or decrease with increasing hydrophobicity. In no case have been described for the previously known derivatives of 2-bromo-2-nitro-propane-1,3-diol with constant biocidal activity improved adhesion to surfaces and applications in crop protection under field conditions.

Object of the invention

The aim of the invention is to find biocidal agents based on 2-bromo-2-nitro-propane-1,3-diol, which enable an economically and ecologically favorable application to plant surfaces under field conditions.

Explanation of the essence of the invention

- Task

The applicability of the known derivatives of 2-bromo-2-nitro-propane-1,3-diol as biocidal agent for the treatment of plant surfaces under field conditions is significantly limited by their good water solubility and / or insufficient adhesion. They are washed out quickly by rain, whereby a reduction of the effect occurs. Derivatives of 2-bromo-2-nitro-propane-1,3-diol with drastically reduced water solubility, on the other hand, can have an insufficient biocidal effect when applied to plant surfaces.

The invention is therefore based on the object to find derivatives of 2-bromo-2-nitro-propane-1,3-diol, which, while maintaining the beneficial biocidal properties of the parent substance by reduced water solubility and improved adhesion to plant surfaces high rainfastness and biocide Allow long term use in field applications.

Features of the invention

According to the invention the object is achieved in that the biocidal agent based on derivatives of 2-bromo-2-nitropropane-1,3-diol oligomers of the general formula 1

о о

II

Br CH ₀ -OCR RCOH ₀ C Br

O C

If

^ (D 3 -H ₂ C ^ "NO ₂

HN 4 -R 1 NH-C-O-R 1 -O-C-NH-R * + NH

O ₀ N ^ CH ₀ -OC OO CO-HpC NO

2 2 Il Il - \ *

Ilι Il 2 'Ι ι Ί R ³ ^ -NH-COR-OC-NH-R " ¹ 4- J η

in addition to customary formulation auxiliaries, where R is a C 1 -C 4 -alkyl radical or an optionally substituted phenyl radical and R ¹ and R ^{2 represent} the intermediates of polyfunctional isocyanates or any polyols and may be the same or different, where η is an integer from 1 to 20 , in particular from 1 to 10, is. The compounds of the invention can be synthesized by known methods by reaction of NCO-terminated prepolymers of polyfunctional isocyanates and polyols with monoesters of 2-bromo-2-nitro-propane-1,3-diol. Suitable isocyanate components of the oligomers are polyfunctional isocyanates such as hexamethylene diisocyanate, 2,4-tolylene diisocyanate and 4,4-diphenylmethane diisocyanate, but also NCO-terminated prepolymers of polyfunctional isocyanates and oligoethylene glycols, polyether alcohols or polyester alcohols. Particularly suitable polyol components of the oligomers according to the invention are oligoethylene glycols, in particular ethylene glycol, diethylene glycol, triethylene glycol and polyethylene glycol (molecular weight 1,000), furthermore polyether alcohols prepared from ethylene oxide or propylene oxide and glycerol, trimethylolpropane or sugar alcohols, or polyester alcohols from dicarboxylic acids and diols or triols.

As the monoester of 2-bromo-2-nitro-propane-1,3-diol, the esters of acetic acid, propionic acid and butyric acid or benzoic acid or their substituted derivatives and optionally substituted phenylacetic acid, phenylpropionic acid or cinnamic acid can be used. For the practical use of such inventive agents, the mixtures of the oligomers of formula 1 with the corresponding diesters of 2-bromo-2-nitro-propane-1,3-diol and optionally 2-bromo-2-nitro-propane-1, 3-diol can be used.

The use of the agents according to the invention is expediently carried out in the preparation or application forms customary for biocides, such as solutions, emulsions, suspensions, concentrations or as dusts or scattering agents. These formulations are prepared using the usual adjuvants such as solvents, carriers, emulsifying and dispersing agents. The agents according to the invention can be used alone or together with other organic or inorganic biocides for controlling phytopathogenic microorganisms.

Surprisingly, it has been found that the foliar application of the invention in foliar application under practical conditions compared to 2-bromo-2-nitro-propane-1,3-diol have a greatly improved rainfastness with the same biocidal activity. By selecting the radicals R, R ¹ and R ² as well as η, the oligomers according to the invention can be optimally varied with regard to water solubility and adhesion to the plant surface while maintaining the biocidal action. The following examples illustrate the invention without restricting it.

example 1

To test the bactericidal activity, holes were punched out uniformly with test bacteria of the genus Erwinia (E. amylovora, E.carotovora pv. Atroseptica, E. carotovora pv. Carotovora) and treated with 0.1 molar (based on the parent substance) solutions or Suspensions of the test substances fed. At certain rating dates, a qualitative assessment of bacterial growth was made. In case of inhibition of the same, the width of the zone of action was determined

 Table 1 shows the good bactericidal action of the substances using the example of the test against Erwinia amylovora.

Example 2

To test the bactericidal activity in foliar application and repeated irrigation, the biocidal agents were prepared as a 20% spray powder and applied as a suspension to the surface of Vicia faba leaves. After the spray coating dried, the leaves were simulated to irrigate for 30 seconds in 1 ml Aquadest. pivoted. To simulate multiple irrigation, this process was repeated up to five times. Before each sprinkling, the leaves were air-dry. The examination of the 0-, 1-, ... 5-time sprinkling on the leaf surface remaining substance coating and the water samples after the 1st, 2nd, ... or 5th Sprinkling on bactericidal activity took place in the agar diffusion test. On the one hand, discs of a defined size were punched out of the treated leaves and seeded on the test bacteria. On the other hand, holes of defined size were punched out of inoculated culture medium and charged with 0.05 ml of the water samples obtained after irrigation. At certain rating dates, a qualitative assessment of bacterial growth was made. In case of inhibition of the same, the width of the zone of action was determined.

Table 2 shows that all preparations have a good bactericidal activity and that, in contrast to the application of the parent substance after application of Oligoaddukte invention even after three or more frequent irrigation on the leaf surface bactericidal activity is detectable.

TABLE 1 Bactericidal action of the oligomers of the formula 1 according to the invention in vitro

R iso- polyol bromine content Bactericidal activity Width of connection cyanate (Wt .-%) Intensity of effective zone Inhibition ^a) (Mm) CH ₃ HMDl " TEG ^cl 20 17 1 C ₆ H ₅ HMDI PEG ^d) 5 + + + 10 2 CH ₃ HMDI SystolT107 ^el 21 + + + 17 3 - - - 40 + + + 17 2-bromo-2-nitro- + + + propane-1,3-diol (known)

a) + + +: complete

+ +: distinct, but not complete +: weak -: none

b) HMDI: hexamethylene diisocyanate

c) TEG: triethylene glycol

d) PEG: polyethylene glycol (molar mass 1 000)

e) Systol T107: polyether alcohol, hydroxy number 410-440

Table 2: Bactericidal activity of oligomers of formula 1 according to the invention in foliar application and repeated irrigation

Ver R iso- polyol bromine Number of irrigation 1 R 2 R 3 R 4 R 5 R binding cyanate salary B + + - \ B H + B H + B + B + + (Wt .-%) h + + + 15 h + + 6 + + + 3 H- - 1 - 0.5 7 + -M 2 H- - 2 H- - 0 0 1 CH ₃ HMDI ^bl TEG ^{C |} 20 h + + + 1 h + + 0 + + 0 Intensity of inhibition ^a) / width of the zone of inhibition (mm) 4 + + ^ 4 + + + 3 + + + + + + + 2 C ₆ H ₅ HMDI PEG ^d) 5 0 h + + + 12 h + + 6 H + 3 H + 1 + + + 1 B 8th + + H 7 H + 5 - 2 - 1 - 3 CH ₃ HMDI Systole 21 + + Η h + + + 10 I- + + 4 H- - 0 - 0 - T107 ^el 10 17 2 0 0 2-bromo-2- - - 40 + + H nitropropane 5 1,3-diol + + ^ (known) 12 + -M 15

a) + + +: complete

+ +: distinct, but not complete +: weak -: none

b) HMDI: hexamethylene diisocyanate

c) TEG: triethylene glycol

d) PEG: polyethylene glycol (molar mass 1000)

e) Systol T107: polyether alcohol, hydroxyl number 410-440 B: leaf surface

R: rainwater

Claims (1)

1. Biocide agent based on derivatives of г-Вгот-г-пКго-ргорап-і, 3-diol for the treatment of plant surfaces under field conditions, characterized in that they are oligomers of general formula 1 0 Q Ti іЗг у0іі _о -0-с-: і? .- σ-ο- :: ₂ σ :: r у '"о о^xcl