JPS5892665A - Substituted benzylimidazolium salt and fungicide - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to fungicides containing novel 'X-substituted benzylimidazolium salts and compounds.

In addition, the present invention uses the compound to control microorganisms such as crab K141. □・・′・N-dodecyl-N,
N-dimethyl-N-benzyl ammonium chloride (
・Wallhäusser (WallhKuBer): ``St.
n-D@m1nf@ktion-Kom-serv1*
rung-Ch@moth*rapl* )”, G*
org ThThlmm5Ver1'(Stuttg
Art Publishing, 1967, p. 222) or 1.3
-bis-(p-inbutylbenzyltwoimidazolium chloride (Federal Republic of Germany patent ti+ 12tt+m
It is well known that the s7 specification) is used to control microorganisms.

By the way, the formula: [In the formula, R1, R8 and Rs are each the same or different and represent a water bulk atom, C1, -C alkyl group or modified halogen atom, and R4 is an alkyl group having 8 to 14 carbon atoms. group, benzyl group, hapgen- or alkyl-substituted benzyl group '4I: R1 represents a water bulk atom or represents an alkyl group, phenyl group, benzyl group having 1 to 8 carbon atoms; , R represents an alkyl group having 1 to 4 carbon atoms or a halogen atom, R7 represents an alkyl group having 1 to 4 carbon atoms or a halogen atom, and X represents a @ group, especially a hydrogen halide It has been found that the substituted benzylimidazoles represented by the following formula have a particularly good action against bacteria, fungi and algae.

C1-C4-alkyl group is, for example, methyl group, ethyl group, butyl group, t-butyl group. R4 is, for example, octyl group, decyl group, dodecyl group, benzyl group, 2-methyl-4-chloro-benzyl group , 2-methyl-3,4-dichloro-pemethyl group, 2-lf&-3-chloro-benzyl group, 2-lf&-3-chloro-benzyl group, 2-lf&-3-chloro-benzyl group, 2-lf&-3-chloro-benzyl group, 2-methyl-3,4-dichloro-pemethyl group, and the atom are, for example, chlorine atom, bromine atom or 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,
It is a group of benbrozoic acid. Preferred are salts of hydrohalic acids.

The novel compound can be prepared, for example, by melting a compound represented by the formula: [In the formula, R4, R%, R6, and RY each represent the above-mentioned ones]. can be obtained by reacting each of the above with a compound shown in Table 1. For example, use a starting quantity of stoichiometry. 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-chlorocubenzyl-4-methyl-5-iodoimidazolium chloride and production of 1-dodecyl-4-methyl-5-iodoimidazole 3
7.9 f t 0.1 mol) was charged and heated to 100°C, and 17.7
f (0.1 mol) was added dropwise. The reaction mixture was heated to 120
Further stirring was carried out at 0-130°C. The compound produced (compound 17) corresponded to the following formula: Hs1 1 \ HI Analysis! ! L: Calculation iI[: Actual value: C51,9852,7 H6,677,1 N 5.85 5.2C11
2,8112,1 123,4622,7゜Example 2 Preparation of 17decyl-3-[2-methyl-3-chlorocubenzyl-4-methyl-5-bromimidazolium chloride 1-decyl-4-methyl-5 -bromimidazole 60
．． 2 F (0.2 mol) was heated to 100 °C, and 35.4 t (0
, 2 mol) was added dropwise. The reaction mixture was heated at 120°C to 1
The mixture was further stirred at 30°C for a while.

This liquid compound (bleeding eyelids 8) corresponded to the following analysis results: Analysis results: Calculation *: Actual value: C55,46 gates, l H6,937,2 N 5.88 5.9 C114,9114 ,1 Br 16.81 15.9Example 3 1.3-di[2-methyl-4-lytetrayl]-benzyl-4-methyl-5-chloroimidazolium chloride production l-[2-methyl-4 -Chlorcubenzyl-4-methyl-5-chloroimidazole 255 f (1 mol) was heated to 80°C, and 4-chlorcubenzyl-orthooxyrylic a'
Lido (2-methyl-4-chloro-benzyl chloride)
175 t (in 1 mo) were added dropwise and the mixture was then further stirred at this temperature for about 1 hour.

A compound (compound 46) 430F with the following composition was produced: l! Column value: Calculated value: C56.5% 55.81 l H5.0g 4.65% N 6.8% 6.5l- C132.1% 33.0 11 Example 4 1-decyl-3-(2 -Methyl-4-chloro)-be/zi-4-methyl-5-chloroimidazolium chloride production 1-decyl-4-methyl-5-chloroimidazole 25
．． 6 t (0,1 mol) was heated to 100°C, and 17.7 f (0,1 mol) of 4-chloro-O-xylyl chloride was added to this.
1. Add 1% Le) dropwise. The mixture was stirred at 125° C. for 30 minutes.

Compound 43F having a melting point of 99°C was produced (Compound 43)e Example 5 1-dodecyl-3-(2-methyl-3-chloro)-1be, fuji-4-methyl-5-chloroimidasol Production of cum chloride l-dodecyl-4-methyl-5-chloroimidazole
14.2 f (0.05 mol) was heated to 95 °C and 3-
8.4 r (o, os) of chloro-O-xylyl chloride was added, and the mixture was further stirred at 95°C for 30 minutes.

A final product 22.6 F with a melting point of 112° C. was produced (compound A5). The yield was quantitative.

Example 6 Preparation of 1-decyl-3-benzyl-4-methyl-5-chloroimidazolium chloride 1-decyl-4-methyl-5-chloroimidazole 25
．． 5 F (0.1 mol) 100″cK+ML, 1
Benzyl chloride 12.6 t (0.1 mol) in 0 minutes
The mixture was then further stirred at 125° C. for 30 minutes.

The final product (compound 41) 38 f (0,1 mos,) 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 wrinkle compound was guaranteed by elemental analysis. Compounds with no physical chemistry description are real r/IA
K can be obtained in the same way as in the case of the obtained compound;
It can be expected to have the same effect as the compound tested in detail 11 due to its similar structure.

Formula: [In the formula, 14. Production of the raw material represented by the formula: [wherein,
R1, R・R? represent the above-mentioned compounds respectively] in a solvent such as dimethylformamide at a temperature of 100°C to 150°C for 1 to 20 hours with Na0CH1
and the CHsOH is distilled off, the product thus obtained is reacted with a compound of the formula: n'-ct, where 84 is as above, and the NaCl is separated from the reaction mixture to form the final product. It is done in such a way that the substance is isolated from the bath salts.

Thus, for example, the following compound is obtained: 8. is +1 S Ha R. Bl boiling range CHHg
HCHs C1178℃-211C/8milino(-le CB! Hfi Hcas CL
175℃-2211: Lev 8 Millino (-R formula: [In the formula, Ha, B@, R? represent the above-mentioned ones respectively] The production of the raw material is, for example, 4-methylindazole and chlorine. gas and under ultraviolet light at 20℃~5
4-Methyl-5-chloroimidazole is converted into the hydrochloride salt by reaction at 0° C. in a solvent such as carbon tetrachloride or monochlorohe/zole for 2 to 10 hours; to alkali, e.g. N
&HCOI isolation.

This compound melts at 130°C to 132°C.

The novel compounds are suitable for the control of microorganisms, for example slime-forming microorganisms in water protection from algae growth, cooling plants, paper industry or humidification installations. Furthermore, is this compound suitable for industrial use? It can be used as a M 11 system or as a preservative, and in case of plant protection as a fungicide.

The following microorganisms can be controlled, for example, with the new active substances: Jitaphyl.5oaeus 5tar.■ (staphylococcus aureus 1i), 1aeh@riehia 5all
(Colon W/i), K1@bsi@11a 11! l-*
jmon1ms, C1trol+aet @r
trmup town-quantity, Prot* ■vu1
girls, Ps*mdom, onas @@rv
timosa (Pus aeruginosa II), Pm*udemonam
flor*se@ms, Xanthomo
mam veil-eaterla, l Xan
thor++onas malvaeearum,
Erwlnlaearotovara, l Er
winia an+ylOvora, Desu
lf mouth vi -brl@desulfuricans
(sulfate-reducing bacteria), Str*p-4ov*rtlc order 1
jum rubr1r@tlau11, muaperg
llusnig@r (black mold), Aapergl
llus vermieol+r.

P@n1a1111uu fullculoauta,
I'aeeilomyeemmaar-negativeot11,
Triehodern+a vIrld*, Ch
aetomiamglobomuIlfI, Can
dlda albreans, G fist otrlahu
maat+dldana, Mon111a 5
1tophlla, 5cea*d amasqu
adrieauda, Chlor@11a v
ulgars, Nostoemume6ru
m.

The new compounds are bathable in water. This compound is therefore preferably used in the form of a water bath solution. rich l
1Iil moxibustion agents can also be obtained in combination with organic solvents, such as ethanol.

Typical concentrations used are i0. o1-1%; oil transportation, bathing areas, RfI
In case of water treatment applications in cooling plants 1, heating equipment, flower preservation means or in the paper industry, active substance amounts of 5 to 100 ppm are sufficient to prevent the development of microorganisms. Ready-made disinfectant solutions contain 0.5-10% (% by weight) of active substance.

In the case of plant preservation, the amount used is 0.1 to 5 k of active substance.
It's y'h a. Preparations with organic solvents can contain active substances 1-601G.

This active substance may be combined with other known fungicides.

In this case, in many cases some of this mixture produces a synergistic effect, resulting in a broadening of the effective spectrum of bactericidal action,
That is, the bactericidal action of the combined product is greater than the sum of the additive actions of the individual components.

Active substances that can be combined with the benzylimidazoles according to the invention are, for example: 2-(thiocyanomethylthiono-benzthiazole, 1-(2-(2,4-dichlorophenyl)-2- ()tetrabenyloxy)-ethyl)-M-imidazole, 2,4,5,6-titrachloroisophthalodinitrile, methylene bisthiocyanate tributyltin oxide, mercaptobenzthiazole, benzisothiazole p7 and its alkali metal salts, N- Alkali metal compound of human axy-N-cyclohexyldiazenium oxide, 2-(methoxycarbonylanno)-benzimidazole, 2-methyl-3-oxo-5-chloro-thiazoline-3
-one, trihydroxymethyl-nitro-methane, glutardialdehyde, trihydroxyacetamide, quaternary ammonium compounds.

In the following tests the following known active substances were used as comparative drugs: Mu: N-dodecyl-N,N-dimethyl-N-benzyl-
Ankylonium chloride (WallhWuB*r): "Sterlissatsuion-Desinfection-Konzerfirungu Hemochi 2B (5tIr amount 11sat-
1on -D**1nf@ktion -Koassr
v1*rong-Chsmot-b*rap! m)
”, G@org Thl@m@ver1mg (
Published by Stuttgart, 1967, 8222
Page) 11:1,3-bis-(p-inbutylbe/zil)
- Indazolimukpurid (German Patent No. 1216487) Test 1 To determine the action of new compounds against 11 AMK, 5 sg of active substance is added to 2x Kll in increasing dilutions in sterile test tubes. Add the reduced broth medium 5- and mix.

Next, 16 hours old bacteria E diluted with 1:IOK
The tubules were inoculated by adding 1@ of seh@rieb1a eoll (E. coli) and this
The temperature is maintained at 37°C for an hour. After this time, the sample is transferred from the tube to the bacterial medium, which is also incubated at 37° C. for 24 hours. After transfer of the sample to the medium, bacterial development no longer takes place: such a dilution step kills! It is described as an I value.

The test results are, for example, compound layer 2, Mu3, Mu4, Mu5,
M9, A10. Jill and 412 are Esehsri-
Known effective substances for chla aoli [B
(for example, a dilution level of 100: 1 million parts by weight).

Test 2 To test the effect on fungi, 1 active substance was added to fungi,
Idl-en 1aeti- or Candida albl
Depending on the growth of eams, 100 parts by weight, 50 parts by weight, 25 parts by weight, 12 parts by weight,
Added in amounts of 6 parts by weight and 3 parts by weight. Sakae I11 solution
Put the active substance mixture 10- into a sterilized test tube, and
m seeds with one drop of a spore suspension containing conidia of O. or 111B spores.

After being kept at constant temperature for 120 hours, samples were taken out from small tubes that showed no visible growth of bacteria and transferred to a soda tray. Dilution JR11it is 4iiiI &! After transferring the sample to the medium, the growth of soda no longer takes place. be done.

The test results show, for example, compounds ll11, A62, mu3,
It shows that A4.45, A9.4 10% All and 412 have a better absorption effect (eg 12:1 million) than the known active substances Mu and II (eg 25:1 million).

Exam 3 Rut 11! To test the action against l1lK, the active substance was added to the unicellular green alga Chler.lla vmlgar.
10 parts by weight, 7.5 parts by weight, 5 parts by weight,
Added in amounts of 2.51 parts by weight and 1 part by weight. Sakae**liquid-
Active substance mixture and nutrient solution (control) each 100-
Put the address in a 300-ml flask. This nutrient solution was added to the algae Chlor@lla vulg-a before adding the active substance.
inoculate with a suspension of ri; cell density is adjusted to 10' cells/nutrient solution. After applying the test patch amount for 10 days at room temperature and under light penetration, the results of the O test show that compounds 42 and A3, for example, have a known active mass and B (e.g. 5:1 million). (e.g. 2.5:1 million) indicates that it has a better convergence effect than that of 56.

Claims (1)

[Scope of Claims] [In the formula, 11, BR and 81 are each the same or different and represent a water 1A atom, a Cl-C4-alkyl group, or a norogen atom, and 凰4 has 8 to 14 carbon atoms. An alkyl group, a benzyl group, a halogen- or alkyl-substituted benzyl group, R'' is a hydrogen atom, or an alkyl group, a phenyl group, a benzyl group having 1 to 8 #2 atoms , R represents an alkyl group or halogen atom having 1 to 4 RX atoms, R7 represents an alkyl group or halogen atom having 1 to 4 *X atoms, and X represents an acid group] (2) Ill represents a hydrogen atom or a chlorine atom, Rs represents a hydrogen atom or a -atomic atom, 81 represents a methyl group, 14 represents a decanyl group or a dodecanyl group, R1
represents a hydrogen atom, Rs represents a methyl group, R1 represents a cell atom, and X represents a chloride group, the claims l! The compound described in Section 1 of the I series. [In the formula, R1, 1m and R1 are each the same or different and represent a bulky atom, a C1-C4-alkyl group, or a tetragen atom, and R4 is an alkyl group having 8 to 14 carbon atoms, a benzyl group , hapgun or alkyl-substituted benzyl group, R1 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, phenyl group, or benzyl group, and RY represents a hydrogen atom having 1 to 8 carbon atoms, and RY represents a benzyl group having 1 to 4 carbon atoms. R7 represents an alkyl group having 1 to 4 carbon atoms or a halogen atom, and X represents an acid group. agent. (4) R1 represents a hydrogen atom or a chlorine atom, 8-rich represents a water bulk atom or a chlorine atom, R1 represents a methyl group, R4 represents a decanyl group or a dodecanyl group, BM represents a water 1A atom, R6 The disinfectant according to claim 3, characterized in that it is a benzylimidazolium salt, which is a compound in which R1 represents a methyl group, R1 represents a chlorine atom, and X represents a chloride group.