JPH0375544B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel and important substituted benzylimidazolium salts and fungicides containing the compounds. Furthermore, the invention relates to a method of controlling microorganisms with said compounds. N-dodecyl-N,N-dimethyl-N-benzyl-ammonium chloride (Wallhaeusser:
Hemoterraby (Sterilization-Desinfektion-)
Kon-servierung-Chemotherapie)”, George
Published by Thieme Verlag (Stuttgart), 1967,
It is known to use 1,3-bis-(p-isobutylbenzyl)-imidazolium chloride (German Patent No. 1,216,487) to control microorganisms. By the way, the formula: [In the formula, R ¹ , R ² and R ³ are each the same or different and represent a hydrogen atom, a C ₁ -C ₄ -alkyl group or a halogen atom, and R ⁴ is an alkyl group having 8 to 14 carbon atoms. , represents a benzyl group, a halogen- or alkyl-substituted benzyl group,
R ⁵ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, a phenyl group, or a benzyl group, R ⁶ represents an alkyl group having 1 to 4 carbon atoms or a halogen atom, and R ⁷ is 1~
Substituted benzylimidazoles of the alkyl group having 4 carbon atoms or a halogen atom, X being an acid group, in particular a hydrohalic acid, have a particularly good action against bacteria, fungi and algae. It was found that the _C1 - _C4 -alkyl groups are, for example, methyl, ethyl, butyl, t-butyl, ^R4 is
For example, octyl group, decyl group, dodecyl group, benzyl group, 2-methyl-4-chloro-benzyl group,
2-methyl-3,4-dichloro-benzyl group, 2
-methyl-3-chloro-benzyl group. A halogen atom is, for example, a chlorine atom, a bromine atom or an iodine atom. Alkyl groups having 1 to 8 carbon atoms are, for example, methyl, ethyl, hexyl, octyl. Acid groups are, for example, inorganic or organic acids, such as hydrochloric acid,
Hydrobromic acid, dodecylbenzenesulfonic acid, acetic acid, salicylic acid, and benbrozoic acid groups. Preferred are salts of hydrohalic acids. The novel compounds may have the formula, for example: [In the formula, R ⁴ , R ⁵ , R ⁶ , and R ⁷ each represent the above-mentioned] compound represented by the formula: It can be obtained by reacting with a compound represented by [wherein R ¹ , R ² , and R ³ each represent the above-described one]. For example, stoichiometric amounts of starting materials are used. The reaction is carried out, for example, in the imidazole melt without solvent. The reaction is carried out at about 50°C to 130°C depending on the melting temperature. Example 1 1-dodecyl-3-[2-methyl-4-chlor]
-Production of benzyl-4-methyl-5-iodoimidazolium chloride 37.9 g (0.1 mol) of 1-dodecyl-4-methyl-5-iodoimidazole was charged, heated to 100°C, and 4-chloro-orthooxy Lyl chloride 17.7
g (0.1 mol) was added dropwise. Add this reaction mixture to 120
Further stirring was carried out at 130°C. The compound produced (compound No. 7) corresponded to the following formula: Analysis result: Calculated value: Actual value: C 51.98 52.7 H 6.67 7.1 N 5.05 5.2 Cl 12.81 12.1 I 23.46 22.7 Example 2 1-decyl-3-[2-methyl-3-chlor]-
Production of benzyl-4-methyl-5-bromimidazolium chloride 60.2 g (0.2 mol) of 1-decyl-4-methyl-5-bromimidazole was heated to 100°C, and 35.4 g of 3-chloro-orthooxylyl chloride ( 0.2 mol) was added dropwise. This reaction mixture was heated to 120°C to 130°C.
The mixture was further stirred for 30 minutes. This liquid compound (compound No. 8) corresponded to the following analysis results: Analysis results: Calculated value: Actual value C 55.46 56.1 H 6.93 7.2 N 5.88 5.9 Cl 14.91 14.1 Br 16.81 15.9 Example 3 1,3-di -Production of [2-methyl-4-chlor]-benzyl-4-methyl-5-chloroimidazolium chloride 1-[2-methyl-4-chlor]-benzyl-4
- 255 g (1 mol) of methyl-5-chloroimidazole was heated to 80°C, 175 g (1 mol) of 4-chloro-orthooxylyl chloride (2-methyl-4-chloro-benzyl chloride) was added dropwise, and then The mixture was further stirred at this temperature for about 1 hour. 430 g of a compound (compound No. 6) with the following composition was produced: Actual value: Calculated value: C 56.5% 55.81% H 5.0% 4.65% N 6.8% 6.51% Cl 32.1% 33.0% Example 4 1-decyl- 3-(2-methyl-4-chloro)-
Production of benzyl-4-methyl-5-chloroimidazolium chloride 25.6 g (0.1 mol) of 1-decyl-4-methyl-5-chloroimidazole was heated to 100°C, and 4-chloro-o-xylyl chloride was added to it. 17.7g (0.1
mol) was added dropwise and the mixture was further stirred at 125°C for 30 minutes. 43 g of a compound with a melting point of 99° C. was produced (Compound No. 3). Example 5 1-dodecyl-3-(2-methyl-3-chlor)
-Production of benzyl-4-methyl-5-chloroimidazolium chloride 14.2 g (0.05 mol) of 1-dodecyl-4-methyl-5-chloroimidazole was heated to 95°C, and 3-
Chlor-o-xylyl chloride 8.4g (0.05mol)
was added dropwise and the mixture was further stirred at 95°C for 30 minutes. 22.6 g of final product with a melting point of 112° C. was produced (Compound No. 5). The yield was quantitative. Example 6 1-decyl-3-benzyl-4-methyl-5-
Preparation of chlorimidazolium chloride 25.5 g (0.1 mol) of 1-decyl-4-methyl-5-chloroimidazole was heated to 100°C, 12.6 g (0.1 mol) of benzyl chloride was added dropwise over 10 minutes, and then this mixture was heated. The mixture was further stirred at 125°C for 30 minutes. 38 g (0.1 mol) of the final product (compound No. 1) was obtained. The yield was quantitative. The compounds listed in the following table were obtained, with corresponding melting points (Fp) listed. The structure of the compound was confirmed by elemental analysis. Compounds for which no physical chemistry description is given can be obtained in the same way as the compounds actually obtained; they can be expected to have the same effect as the compounds tested in detail due to their similar structure. .

[Table] Formula: [In the formula, R ⁴ , R ⁵ , R ⁶ , and R ⁷ each represent the above] is produced by the formula: [In the formula, R ⁵ , R ⁶ and R ⁷ each represent the above-mentioned compounds] is dissolved in a solvent such as dimethylformamide at a temperature of 100°C to 150°C for 1 to 20 minutes.
After reacting with NaOCH ₃ for an hour and distilling off the CH ₃ OH, the product thus obtained has the formula: R ⁴ ~Cl, where R ⁴
represents the above-mentioned compound],
This is done in such a way that the NaCl is separated from the reaction mixture and the final product is isolated from the solvent. Thus, for example, the following compounds are obtained:

[Table] 8mbar formula: [In the formula, R ⁵ , R ⁶ , and R ⁷ each represent the above-mentioned material] can be produced by, for example, 4
- Methylimidazole and chlorine gas in ultraviolet light
4-
The process is carried out by converting to the hydrochloride of methyl-5-chloroimidazole and isolating 4-methyl-5-chloroimidazole from the hydrochloride with an alkali, for example NaHCO ₃ . This compound melts at 130°C to 132°C. The new compounds are suitable for the control of microorganisms, for example for the protection of water from algae growth, for the control of slime-forming microorganisms in reflux cooling plants, the paper industry or humidification installations. Furthermore, this compound can be used as a disinfectant or preservative for the industrial scope and as a fungicide in the case of plant protection. The following microorganisms can be controlled, for example, with the new active substances: Staphylococcus aureus,
Escherichia coli, Klebsiella
pneumoniae, Citrobacter freundii, Proteus
vulgaris, Pseudomonas aeruginosa,
Pseudomonas fluorescens, Xanthomonas
vesicatoria, Xanthomonas malvacearum,
Erwinia carotovara, Erwinia amylovora,
Desulfovibrio desulfurieans (sulfate reducing bacteria),
Streptoverticillium rubrireticuli,
Aspergillus niger (black mold), Aspergillus
versicolor, Penicillium funiculosum,
Paecilomyces variotii, Trichoderma viride,
Chaetomium globosum, Candida albicans,
Geotrichum candidans, Monilia sitophila,
Scenedesmus quadricauda, Chlorella,
vulgaris, Nostoc muscorum. The new compounds are readily soluble in water. This compound is therefore preferably used in the form of an aqueous solution. Concentrated preparations can also be obtained in combination with organic solvents, such as ethanol. Typical usage concentrations are 0.01-1% of active substance based on the weight of the material to be protected; used for water treatment in petroleum transport, bathing areas, reflux cooling plants, humidification installations, flower preservation means or the paper industry. In some cases, amounts of active substance from 5 to 100 ppm are sufficient to inhibit the development of microorganisms. Ready-made disinfectant solutions contain 0.5-10% (% by weight) of active substances. In the case of plant protection, the amount used is from 0.1 to the active substance
5Kg/ha. Preparations with organic solvents are
It can contain from 1 to 60% of active substance. This active substance may be mixed with other known fungicides. In this case, a widening of the effective spectrum of fungicidal action is obtained, in which some of these mixtures often produce a synergistic effect, i.e. the fungicidal action of the combined product is greater than the sum of the added actions of the individual components. big. Active substances that can be combined with the benzylimidazole according to the invention are, for example: 2-(thiocyanomethylthio)-benzthiazole, 1-[2-(2,4-dichlorophenyl)-2-
(propenyl-oxy)-ethyl]-1H-imidazole, 2,4,5,6-tetrachloro-isophthalodinitrile, methylene bisthiocyanate tributyltin oxide, mercaptobenzthiazole, benzisothiazolone and its alkali metal salts, N'- Alkali metal compound of hydroxy-N-cyclohexyl-diazenium oxide, 2-(methoxy-carbonylamino)-benzimidazole, 2-methyl-3-oxo-5-chloro-thiazolin-3-one, trihydroxymethyl-nitro -methane, glutardialdehyde, chloracetamide, quaternary ammonium compounds. In the following tests the following known active substances were used as comparative drugs: A: N-dodecyl-N,N-dimethyl-N-benzyl-ammonium chloride (WallhauBer: Sterilization
Desinfektion−Konservierung−
Chemotherapie)”, Georg Thieme Verlag
(Published by Stuttgart, 1967, p. 222) B: 1,3-bis-(p-isobutylbenzyl)-
Imidazolium chloride (German Patent No. 1 216 487) Test 1 To determine the action of new compounds against bacteria, double the amount of active substance in 5 ml of increasing dilution in sterile test tubes. Add 5 ml of concentrated broth medium and mix. Next, 1:10 diluted 16-hour-old bacterial strain Escherichia coli (E. coli) was used.
Inoculate this tubule by adding drops;
This is kept constant at 37°C for 24 hours. After this time,
Transfer the sample from the small tube to the bacterial medium, which was also incubated for 24 hours.
Maintain constant temperature at 37°C for an hour. The dilution step at which bacterial development no longer takes place after transfer of the sample to the medium is described as the bactericidal value. The test results are, for example, Compound No. 2, No. 3, No.
4, No.5, No.9, No.10, No.11 and No.12
This shows that it has a better bactericidal effect against Escherichia coli (eg, dilution level 12: 1 million parts by weight) than the known active substance B (eg, dilution level 100: 1 million parts by weight). Test 2 In order to test the effect on fungi, the active substance was tested on the fungi Aspergillus niger, Oidium
Depending on the growth of lactis or Candida albicans, 100 parts by weight, 50 parts by weight per million parts by weight of nutrient solution,
It is added in amounts of 25 parts by weight, 12 parts by weight, 6 parts by weight and 3 parts by weight. Place 10 ml of the nutrient solution-active substance mixture into a sterile test tube and inoculate with 1 drop of the spore suspension containing 10 ⁶ conidia or cells. 120
After maintaining the temperature for an hour, a sample is taken from a small tube showing no visible bacterial growth and transferred to a bacterial culture medium.
After transferring the sample to the medium, a dilution stage is identified in which bacterial growth no longer takes place. The test results are, for example, Compound No. 1, No. 2, No.
3. No. 4, No. 5, No. 9, No. 10, No. 11 and No. 12 have better bactericidal action (e.g. 12 : 1 million). Test 3 To test the effect on green algae, the active substance was added to a phosphate-rich nutrient solution that promotes the growth of the unicellular green algae Chlorella, vulgaris at 10 parts by weight, 7.5 parts by weight, 5 parts by weight per million parts by weight of the nutrient solution. Parts by weight, 2.5
It is added in amounts of 1 part by weight and 1 part by weight. Nutrient solution
Active substance mixture and nutrient solution (control) respectively
Pour 100ml into a 300ml flask. This nutrient solution was added to the algae Chlorella vulgaris before the addition of the active substance.
cell density is adjusted to 10 ⁶ cells/ml of nutrient solution. The effect is evaluated after the test batches have been kept under light penetration at room temperature for 10 days. The results of the tests show that, for example, compounds No. 2 and No. 3 have a better algicidal action (for example, 2.5:1 million) than the known active substances A and B (for example, 5:1 million).
Show that.

Claims (1)

[Claims] 1 Formula: [In the formula, R ¹ , R ² and R ³ are each the same or different and represent a hydrogen atom, a C ₁ -C ₄ -alkyl group or a halogen atom, and R ⁴ is an alkyl group having 8 to 14 carbon atoms. , represents a benzyl group, a halogen- or alkyl-substituted benzyl group,
R ⁵ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, a phenyl group, or a benzyl group, R ⁶ represents an alkyl group having 1 to 4 carbon atoms or a halogen atom, and R ⁷ is 1~
represents an alkyl group having 4 carbon atoms or a halogen atom, and X represents an acid group]. 2 R ¹ represents a hydrogen atom or a chlorine atom, R ² represents a hydrogen atom or a chlorine atom, R ³ represents a methyl group, R ⁴ represents a decanyl group or dodecanyl group, R ⁵ represents a hydrogen atom, 2. The compound according to claim 1, wherein R ⁶ represents a methyl group, R ⁷ represents a chlorine atom, and X represents a glolide group. 3 formula: [In the formula, R ¹ , R ² and R ³ are each the same or different and represent a hydrogen atom, a C ₁ -C ₄ -alkyl group or a halogen atom, and R ⁴ is an alkyl group having 8 to 14 carbon atoms. , represents a benzyl group, a halogen- or alkyl-substituted benzyl group,
R ⁵ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, a phenyl group, or a benzyl group, R ⁶ represents an alkyl group having 1 to 4 carbon atoms or a halogen atom, and R ⁷ is 1~
A disinfectant containing a benzylimidazolium salt represented by the following formula: an alkyl group having 4 carbon atoms or a halogen atom, and X represents an acid group. 4 R ¹ represents a hydrogen atom or a chlorine atom, R ² represents a hydrogen atom or a chlorine atom, R ³ represents a methyl group, R ⁴ represents a decanyl group or a dodecanyl group, R ⁵ represents a hydrogen atom, The disinfectant according to claim 3, which contains a benzylimidazolium salt, which is a compound in which R ⁶ represents a methyl group, R ⁷ represents a chlorine atom, and X represents a chloride group.