DD234782A1 - BIOZIDE MEDIUM - Google Patents

Abstract

The invention relates to biocidal agents for combating unwanted algae, fungal and bacterial growth in water cycles. As active ingredients they contain compounds of the general formula R-CHCH-NO 2 and R 1 are nitro, hydroxy, halogen or hydrogen, R 2 is nitro or hydrogen and R 3 is nitro, halogen, methoxy, alkylamino or hydrogen.

Description

or

and R _{1 is} nitro, hydroxy, halogen or hydrogen, R _{2 is} nitro or hydrogen and R _{3 is} nitro, halo, methoxy, alkylamino or hydrogen.

Field of application of the invention

The invention relates to agents for controlling algae, fungi and bacteria in water systems.

Characteristic of the known technical solutions

It is known that objects and equipment that are under water for a long time, z. As on inruns and pipelines for industrial cooling water, underwater structures and power plants, accumulate a lot of living organisms in the water, multiply and lead to significant disabilities. A major problem in water systems is the formation of algae and their rapid growth with formation of algae grass. In warmer water cycles also slime molds and bacteria, which lead to the formation of the skin and also represent a considerable disturbance factor in water cycles, multiply.

For algae control mainly quaternary ammonium halides (quats) are used, for. B. Alkyi-trimethyl-ammonium-halides, dialkyl-dimethyl-ammonium-halides and alkylbenzyl-dimethyl-ammonium-halides. These quats have the disadvantage that they have a too low spectrum of activity against different species of algae and are practically ineffective against slime molds and bacteria.

In DE-PS 2 455 392 a ^ '- dibromo-succinimides are claimed as agents against organisms living in water. These agents have too little effect, especially against algae, and have led to no practical application. In US Pat. No. 3,309,191, ω-nitrostyrenes having an accumulation of nitro and halogen atoms in the molecule are claimed as herbicides which likewise have not found any practical application.

Object of the invention

The aim of the invention is to develop new biocidal agents which have a broad spectrum of activity in water cycles, are economically advantageous and toxicologically harmless.

Explanation of the essence of the invention

This object is achieved in that the biocidal agent in addition to conventional excipients and carriers as active compounds of the general formula

R-CH = CH-NO ₂ , in the R

or

and R, nitro, hydroxy, halogen or hydrogen, R _{2 is} nitro or hydrogen and R _{3 is} nitro, halo, methoxy, alkylamino or hydrogen. The compounds are prepared in known manner from the corresponding aromatic aldehydes and nitromethane. ·

Examples of the agents according to the invention are the compounds compiled in Table 1.

Table 1: R-CH = CH-NO ₂

Substance R melting point in ⁰ C

A furyl 72 B thienyl 76-78 C C ₆ H ₅ - 58 D 2-NO ₂ -C ₆ H ₄ - 102-104 e 3-NO ₂ -C ₆ H ₄ - 128 F 4-NO ₂ -C ₆ H ₄ - 192-194 G 2-Cl-C ₆ H ₄ - 47 H 4-CI-C ₆ H ₄ - 110 I 2-OH-C ₆ H ₄ - 132-133 J 4-CH ₃ OC ₆ H ₄ - 85 K 4-N (CH, L-O = H, - 181

The compounds according to the invention are suitable for controlling green algae of the Chlorella vuigaris type and for controlling algae mixtures. Furthermore, they are characterized by a good fungicidal and bactericidal action.

embodiments

Example 1: Test on the green alga Chlorella vuigaris

The substances are added in the form of a dimethylformamide solution in a suspension of freshly drawn algae spores in nutrient solution. The suspension density was 4 million cells / ml. The algae are cultivated for 6 h under optimal conditions.

The relative inhibition of algae growth compared to the untreated control was determined.

The parameter used is the change in the absorption of the light at 680 nm by the algal suspension. This absorption is proportional to the chlorophyll content and approximately proportional to the growth of the algae.

The results are shown in Table 2.

The substances A to K are in all tables for the compounds listed in Table 1, L is the comparative product (dimethyl-alkyl-benzyl-ammonium-chiorid).

10 " ⁶ m

Table 2: Action against Chlorella vuigaris concentration 1 · substance 5 · 10 ^β Μ 35 2.5-10- ⁵ M 94 36 A 100 93 65 B 100 100 35 C 100 100 23 D 100 100 90 E - 100 100 78 F 100 100 60 G 100 100 30 H 100 62.5 0 I 100 63 0 J. 100 64 L 100

From Table 2, the very good effect of the inventive composition over the comparative product L can be seen, with the substances C, F, G and H stand out especially.

Example 2: Test on mixed algae cultures

Algae of various origins were pre-cultivated and used to inoculate the test cultures. The nutrient solution was the method developed by Kühl-Lorenzen, modified by Böhm in 1970. The compounds of the invention are applied in the nutrient solution, and after mixing is inoculated with the algae mixture from the preculture.

The evaluation of the effectiveness took place via the credit score 1-5.

Where:

1 - thick, closed algae cover, very good growth of algae

2 - closed algae cover, good algae growth

3 - Algae growth discernible, inhibited algae growth

4 - Algae are barely recognizable without optical aids

5 - without opt. Aids no algae recognizable

Table 3: Effect on algal mixed cultures Substance Concentration

10 mg / l 5 mg / l 2 mg / l

A 4-5 3 3 B 5 4 2-3 C 5 5 4 D 5 4-5 4-5 e 5 4-5 F 5 4-5 4 G 5 3 3 H 5 5 4-5 I 5 4-5 3 J 5 4-5 3 K 5 5 4-5 L 3 1 1 Dimanin A 3 1 1

Table 3 shows the superior effect of all agents according to the invention on mixed algae cultures for Comparative Product L and for the commercial product Dimanin A (Bayer AG).

Example 3: Test on ascomycetes

Still liquid agar is mixed in appropriate concentrations with the active ingredient and filled into sterile Petri dishes.

After cooling, the agar plates are inoculated with a mycelium spore suspension of the corresponding fungi and for 10 days

24 ⁰ C beb rütet. The evaluation is done visually by rating. The credit score 4 is a very good one

Effect and the credit score 1 no effectiveness.

Table IV shows the effectiveness of the agents according to the invention in three different concentrations against Botrytis cinerea, Alternaria tenuis and Fusarium culmorum. The order of substances again corresponds to that of Table 1.

Alternaria tenuis Fusarium culmorum

4 4

4 4

1 1

4 4

4 4

3 3

4 4 4 4 4 4 4 4 4 4

1 1 -

4 4

4 4

4 4

4 4

4 4

1 1

4 4:

4 4

1 1

4 4

4 4

4 4

4 4

4 4

4 4

3 4 1 1

4, 4 4 4 1 3

Table IV: % Active ingredient Botrytis cinerea substance 0.1 4 A 0.01 4 0.001 1 ' 0.1 4 B 0.01 4 0.001 3 0.1 4 C 0.01 4 0.001 4 0.1 4 D 0.01 4 0.001 4 0.1 4 e 0.01 4 0.001 4 0.1 4 G 0.01 4 0.001 4 0.1 4 H 0.01 4 0.001 1 0.1 4 I 0.01 4 0.001 4 0.1 4 J 0.01 4 0.001 2 0.1 4 Ridomil 0.01 4 0.001 3 0.1 4 Maneb 80 0.01 4 0.001 3

Table IV shows the same good and better efficacy of the compositions of the invention compared to the standards Ridomii and Maneb, wherein the substances C, D, E, G and I stand out particularly.

Example 4 Test on yeast-like fungi (Torulopsis) and bacteria (Erwinia carotovorum var. Atroseptica) Shake cultures of Torulopsis H 24 and Erwinia carotovorum var. Atroseptica were exposed for 6 hours to the compositions according to the invention. Throughout the trial, the growth of Torulopsis H24 and E. c. by optical density measurement

tracked. The growth inhibition is given as a function of the concentration of the means in percent.

Table V shows the growth inhibition of Torulopsis H24 and E. c. by the agents according to the invention.

The substance numbers correspond again to those of Table I.

Table V: Growth inhibition on Torulopsis H24 and Erwinia carotovorum var. Atroseptica (E.c.)

Substance concentration in Torulopsis growth inhibition in%

ppm H 24 E. c.

A 100 100 100

10 100 100

1 21 0

B 100 100 90

10 90 90

: 1 ·. 0: 0

C 100 100 100

10 100 100

1 61 76

D 100 100 100

10 100. 0

1 100 0

E 100 100 100

10 100 100

1 23 17. '

F 100 100 100

10 100 100

1 100 19

G 100 100 100

10 100 100

 1 '93 16

H 100 100 100

10 100 100

1 86 37

I 100 100 100

10 100 100

1 70 75

J 100 100 100

10 100 100

1 33 25

K 100 100 99

10 100 92

1 12, 78

Maneb 100 100

10 13

1 o., - '.

Table V shows that the standard Maneb very good action against yeast-like fungi with simultaneous activity against bacteria (E. c).

Claims (1)

Invention claim: Biocidal agents, in particular for controlling unwanted growth of algae, fungi and bacteria in water cycles, characterized in that they contain, in addition to customary auxiliaries and excipients, compounds of the general formula R-CH = CH-NO ₂
in the R O-