DE2538016A1 - Fungicides and bactericides for technical or agricultural use - contg. hydroquinone monophenyl ether derivs. - Google Patents

Abstract

New agents contain cpds. of formula (I): (where R is H, 1-4C alkyl or opt halo-substd 2-4C acyl; and X, Y and Z are H, halogen, halo-alkyl 1-4C alkyl, 1-4C alkoxy, 1-4C alkylthio, NO2 or amino). (I) show good activity against injurious fungi on technical substrates and against phytopathogenic fungi and bacteria in plant protection. In the plant protection sector, (I) show activity against e.g. true mildews, rusts, Peronspora viticola, Piricularia oryzae and Cladosporium fulvum. In the technical sector, (I) can be used as fungicides and/or bactericides for the preservation of glues, dyes, paints, sealing compounds, textiles, leather, wood and paper, and as disinfectants, in e.g. medical soaps and hand wash pastes.

Description

Fungicidal and bactericidal agents The invention relates to fungicidal and bactericidal agents which are characterized by a content of compounds of the general formula in which R is hydrogen, a (C1-C4) -alkyl radical or a (C2-C4) -acyl radical which is optionally substituted by halogen and X, Y, Z independently of one another are hydrogen, halogen, haloalkyl, (C1-C) -alkyl, (C1 -C4) -Alkoxys (C1-C4) -alkylthio, nitro or amino.

The compounds of the formula I and their preparation are in part in the DOS 16 68 896, 21 36 828 and 22 23 894 as well as in the German patent application P 24 33 o66.3 described as precursors of biologically active compounds, however their own specific biocidal effectiveness was previously unknown. You let yourself according to the provisions of the above applications also z.

B. after J. Am. Chem. Soc. 61, 2702-2704 (1939) or Chem. Abstracts 54, column lo, 922 h (1960).

The compounds have an excellent effect against harmful fungi on technical substrates as well as against phytopathogenic fungi and bacteria in crop protection. So the compounds show a very good effect z. B. against powdery mildew species, Rust fungi, Peronospora viticela, Piricularia oryzae and Cladosporium fulvum.

The fungicidal and bactericidal agents according to the invention can be used in Usually as dusts, wettable powders, dispersions, emulsion concentrates or Granules are formulated. Their total active ingredient content is preferably lo - 90% by weight. In addition, they contain the usual adhesive, wetting, dispersing, filling and Carrier materials.

The compounds of the formula I can also and advantageously be used as fungicides and / or bactericides in the technical field for the preservation of glues, paints, Lacquers, sealants, textiles, leather, wood, paper and as disinfectants z. B. used in medicinal soaps and hand washing pastes and to this Purposes added to the carrier materials or applied to them.

In the following table I are already known under the invention falling preparations listed; the numbers given in the last column mean: 1 = DOS 16 68 896 2 = DOS 21 36 828 3 = DOS 22 23 894 4 = patent application P 24 33 o66.3.

Tables II, III, IV contain methods known per se produced new compounds of formula 1.

PREPARATION EXAMPLES Table I Example XYZR quote No. 1 4-FHHH 1 2 4-Cl HHH 1 3 4-Br HHH 1 4 4-JHHH 1 5 4-OCH3 HHH 1 6 4-CF3 HHH 4 7 4-CH3 HHH 2 8 4-CH3S HHH 2 9 4-NO2 HHH 1 10 4-CF3 2-Cl HH 4 11 4-CF3 2-Br HH 4 12 2-Cl 4-CF3 H CH3 4 13 4-C1 3-C1 HH 2 14 2-C3H7 (i) 5-CH3 HH 2 15 4-Cl HH CH5 1 16 4-NO2 HH CH3 1 17 4-NH2 HHH 1 18 4-Cl 2-Cl HH 2 The following were also produced according to the regulations mentioned: Table II Example XYZR Fp. (Kp) No. (° C) 19 4-Cl 2-NO2 H CH3 55-57 20 4-Cl 2-CF3 HH 82-84 21 4-Cl 2-NO2 HH 89-91 22 4-NO2 2-Cl HH 155-56 23 4-CF3 2-NO2 H CH3 51-52 24 H 2-NO2 HH 105-06 24a 4-Cl H 3'-CH3 H bp 0.1 146 ° Furthermore, many of the compounds of the general formula I can be converted into one another in a manner known per se. Thus, the following substances of the formula I were obtained by reducing the nitro group in compounds of Tables I and II by means of the instructions given: Table III Example YYZR Fp. (Kp) No. 25 4-C1 2-NH2 H CH3 44-47 26 4-CF3 2-NH2 H CH3 76-77 27 4-Cl2-NH2 HH 124-26 28 4-NH2 2-Cl HH 154-55 29 H2-NH2 HH 180-81 On the other hand, compounds of the general formula I in which R is hydrogen can be removed in a manner known per se by alkylation or acylation. In this way, for example, substances in Table 1 are used to obtain those in Table IV below.

Table IV Example XYZR m.p./Kp/nD Nr (° C) 30 4-Cl 2-Cl H COCCl2CH3 nD23 1.5793 31 H 4-Cl H COCCl2CH3 nD23 1.5793 32 4-C1 HH COCH2CH3 Kpo, 1 134-135 33 4-Cl 2 -Cl H COCH3 bp 0.1 146-147 34 4-Cl 2-Cl H COCH2CH3 bp 0.1 158-160 35 4-C1 2-C1 H COCH2C1 m.p. 77-78 36 4-Cl 2-Cl H COCHBrCH3 KP0, 1 185-186 BIOLOGICAL EXAMPLES In the following examples the letters A to G stand for the comparative agents mentioned below: A Benzimidazolcarbamic acid methyl ester + Tetra methyl thiuramdi sulfide B Tetrahydro-3,5-dimethyl-2H-1,3,5-thiadiazine 2'-thione C chloracetaldehyde disulfite D chloroacetamide + quaternary ammonium compounds E 2-methyl-5,6-dihydro-4H-pyran-3-carboxylic acid anilide (pyracarbolide) F 2-methyl-5,6-dihydro-3-cavboxanilido-1 , 4-oxathiindioxid (oxycarboxin) G N- (trichloromethylthio) phthalimide (Folpet) The following application examples show the excellent fungicidal or bactericidal action of the compounds according to the invention in comparison with commercially available comparative agents.

For example I - IV (fungi and bacteria from the technical area) The fungi Pullularia pullulans and Aspergillus were used as representative organisms niger, Penicillium funiculosum, Chaetomium globosum, Alternaria consortiale as well various types of bacteria such as E. coli, Bacterium prodigiosum and Bacterium pyocyaneum selected.

Example I: 0.02 ml each of a bacterial suspension of E. coli were drop-shaped in Petri dishes on nutrient medium (standard I-Nåhragar for bacteria) applied; der: C, ar were previously the solid substances in the liquid state concentrations given in Table 1 have been added.

The plates inoculated with bacteria were evaluated after 4 days, the inhibition of growth compared to the control (= inoculated Agar without added active ingredient = 0% inhibition) rated.

Commercially available mercury-free products were used as comparison means (A, B, C, D), which were used with the same active ingredients as the claimed compounds.

Table I. Compound inhibition in% of E. coli bacteria according to mg active ingredient / liter agar Example 1000 500 100 24 100 75 25 26 100 75 50 25 100 100 50 2 100 100 75 (A) 50 25 (B) 50 25 (C) 100 50 (D) 50 25 Example II: In each case 0.02 ml of a spore suspension of Alternaria consortiale were applied drop-shaped in Petri dishes to nutrient medium (Biomalz agar for fungi); The claimed compounds had previously been added to the agar in the liquid state in the concentrations given in Table II. 6 days after inoculation of the plates, the diameter of the fungal colonies on the agar was measured and the growth inhibition caused by the preparations, expressed in% based on the control (inoculated agar without added active ingredient = 0% inhibition), was determined. Commercially available mercury-free products (A, B, C, D), which were used with the same active ingredients as the claimed compounds, were used as comparison agents.

Table II Compound inhibition in by Alternaria consortiale according to mg active ingredient / liter agar Example 1000 500 100 50 10 5 1 27 100 80 50 25 100 90 70 50 6 100 90 50 20 100 60 30 11 100 39 20 2 100 60 30 100 90 80 50 31 100 90 80 50 (A) 100 27- (B) 100 20 - - (c) 100 60 - - - (D) 100 80 - - - Example III: In each case 0.02 ml of a spore suspension of Aspergillus niger were applied drop-shaped in Petri dishes to mixing soil (Biomlz agar for fungi); The claimed compounds had previously been added to the agar in the liquid state in the concentrations given in Table III. 6 days after inoculation of the plates, the diameter of the fungal colonies on the agar was measured and the growth inhibitions caused by the preparations, expressed in% based on the control (inoculated agar without added active ingredient = 0% inhibition), determined. Commercially available mercury-free products (A, B, C, D), which were used with the same active ingredients as the claimed compounds, were used as comparison agents.

Table III Compound inhibition in% of Aspergillus niger at according to mg active ingredient / liter agar Example 1000 500 100 50 10 5 6 100 90 80 60 20 100 90 80 2 100 60 (A) 100 75 50 - - (B) 100 80 30 - - (C) 100 60 10 - - (D) 40 - - - - - Example IV: Mycelium pieces (diameter 0.5 cm) of the fungus Poria monticola were placed in Petri dishes on nutrient medium (organic malt agar for fungi) in the center; The claimed compounds had previously been added to the agar in the liquid state in the concentrations given in Table IV. 8 days after inoculation of the plates, the diameter of the fungal mycelium on the agar was measured and the growth inhibition caused by the preparations, expressed in d10 based on the control (inoculated agar without added active ingredient = 0% inhibition), was determined. A commercially available mercury-free product (A), which was used with the same active substance as the compounds claimed, served as the comparison agent.

Table IV Compound Inhibition in% of Poria monticola according to mg active ingredient / liter agar Example 500 100 50 10 5 6 - 100 80 - - 18 - 100 80 60 20 (A) 50 44 - - - As can be seen from Tables I-IV, the claimed compounds are considerably superior to the known mercury-free comparison agents in terms of bactericidal and fungicidal action.

Example V: Wheat plants were treated with aqueous suspensions of the claimed Compounds from example (6) and (12) in the use concentrations of 500, 250, 120, 60 and 30 mg of active ingredient per liter of spray liquor treated until dripping wet. As a means of comparison served E and F.

After the active ingredient coating had dried on, the plants became spore of the brown rust of wheat (Puccinia triticina) inoculated and dripping wet in a climatic chamber with 2000 and 100% relative humidity. The plants came 24 hours later returned to a greenhouse and were here 14 days after inoculation for infestation Wheat brown rust examined. The degree of infestation was expressed in% of infested leaf area, based on untreated, infected control plants (= 100% infestation).

Table V Compound% leaf area infested with brown rust according to mg active ingredient / liter spray liquid Example 500 250 120 60 30 6 0 0 0 0 3 20 0 0 0 0 3 (E) 0 0 5 15 35 (F) 0 0 10 25 40 untreated infected 100 plants Example VI: Vine plants grown from cuttings of the Pernospora-susceptible Hurgau were treated to runoff with watery suspensions of the claimed compounds from Examples (11) and (21). The concentrations used were 500, 250, 120, 60 and 30 mg of active ingredient per liter of spray liquor. As a comparison agent, G was used in the same active ingredient concentrations as the test preparations.

After the spray coating had dried on, the plants were treated with a Zoosporangia suspension of Peronospora viticola inoculated and dripping wet in a Climatic chamber at a temperature of 20 ° C and a relative humidity of 100% made. After 24 hours, the infected plants were placed in the climatic chamber taken and placed in a greenhouse with a temperature of 23 ° C and a humidity brought about 80 - 90%.

After an incubation period of 7 days, the plants were moistened placed in the climatic chamber overnight and caused the disease to break out. The infestation evaluation was then carried out. The degree of infestation became more infested Leaf area expressed in comparison to the untreated, infected control plants and is shown in Table VI. As can be seen therefrom, the claimed compounds have an excellent, the comparative means G superior effectiveness.

Table VI Compound% downy mildew at mg active ingredient / liter according to the spray mixture Example 500 250 120 60 30 11 0 0 3 5 15 20 0 0 0 3 5 (G) 0 3 5 10 35 untreated infected 100 plants

Claims (2)

Claims Oil, fungicides and bactericidal agents characterized by a content of compounds of the general formula in which R is hydrogen, a (C1-C4) -alkyl radical or a (C2-C4) -acyl radical which is optionally substituted by halogen and X, Y, Z independently of one another are hydrogen, halogen, haloalkyl, (C1-C4) -alkyl, (C1 -C4) -alkoxy, (C1-C4) -alkylthio, nitro or amino. 2) Use of the compounds of formula I for preserving Glues, paints, varnishes, sealants, textiles, leather, wood, paper and as Disinfectants.