JPS63122674A - Benzimidazole compound - 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 Field of the Invention The present invention relates to a series of benzimidazole compounds, their use as pest control agents, compositions containing them and processes for their synthesis.

[Conventional technology]

Eeo (Agric, Biol, chem,,
46# 171 591982) discloses that benzimidazoles with a terpenoid residue in position 1 have insecticidal activity.

The inventors have found that a series of related compounds have interesting acaricidal and insecticidal activity; many of these compounds also have fungicidal and nematicidal activity. ] The present invention provides compounds of the formula [wherein R1 is methyl optionally substituted with chlorine or 1 or 2 fluorine atoms, H2a, R
za are the same or different, hydrogen, chlorine, bromine, fluorine,
Alkyl having 1 to 4 carbon atoms optionally substituted by 1 or 2 fluorine or chlorine atoms, 1 to 4
optionally substituted by alkoxy having 1 to 4 carbon atoms, acyl having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, nitro, cyan, alkyl having 1 to 4 carbon atoms amino or alkanoyl having 1 to 4 carbon atoms; R3 is hydrogen or alkylte having 1 to 4 carbon atoms; I>V
), A is a group X -Y -R' or 7. [Group CR5R' Te, provided that X is nitrogen, CM 1 fs Ire C (
P,') (wherein R7 is alkyl having 1 to 6 carbon atoms) and Y is oxygen, sulfur or a group NR8 (wherein R8 has 1 to 8 carbon atoms) hydrocarbyl) and R4 is acyl having 1 to 4 carbon atoms or alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, 1
hydrocarbyl having 1 to 10 carbon atoms optionally substituted by acyl having ~4 carbon atoms Z or halogeno, or when X is nitrogen, R' is also hydrogen and R5 is hydrogen, chlorine, Bromine, fluorine, Cney4
selected from alkyl, cl-8 plucoxycarbonyl, alknyl having 1 to 4 carbon atoms and acyl having 1 to 8 carbon atoms; R6 is hydrogen, chlorine, bromine, fluorine and 1 to 4 carbon atoms; A compound or an acid addition salt thereof selected from A/A, 7.1%, or an acid addition salt thereof.

Conveniently R1 is a methyl group. H2a~R2
Only 1 or 2 of 4 is other than hydrogen, such as nitro, methyl,
Preferably it is selected from methoxy and chlorine.

Preferably R3 is methyl.

In one preferred embodiment, A is the group NOR8 with the proviso that R8
is alkyl having 1 to 4 carbon atoms, most preferably hydrogen or methyl.

Preferred compounds include 1-(2(E)-7,7-dichloro-3-methylhepta-2,6-genyl]-2-methylbenzimidazole, 1-[2(1)-6-nodoximino-6- methylhex-2-enyl]-2-methylbenzimidazole, t6B)-6-methyl-8-(2-methylbenzimidazol-1-yl)-1-phenylocta-2,6-dien-1-one, 1- [3-Methylhepta-2,6-dienyl)-2-methylbenzimidazole, 1-[hepta-2,6-dienyl)-2-methylbenzimidazole, (2E)-2-methyl-1-(6-methylocta -2,
6-genyl)benzimidazole and 2-methyl-1-C(2E)-3-methyl-6-benzyloxyiminohex-2-enyl]benzimidazole.

Compounds of formula (1)It exist as geometric isomers with respect to the side chain double bond or bond attached to the 1-position of the imidazole ring. The invention provides the respective isomers and mixtures thereof.

Hydrocarbyl refers to hydrocarbon residues such as alkyl, alkenyl, alkynyl, aryl or aryl substituted alkyl, alkenyl or alkynyl or aryl substituted by alkyl, alkenyl or alkynyl.

When the above molecules have one or more asymmetric centers, the individual optical isomers or mixtures thereof are within the scope of the invention.

The present invention is based on the formula (a) (R1 is the term vchv as defined above, R"R"-R2
The compound having the group CH2CH-c(R3)(an2)2cH-A w 4
(t)) When A or NOR7 or CR5R', a compound having the formula, a suitable hydroxylamine or a Wittig reagent [e.g., (R9)3P- CR"R' (However, R5 and R6
is as defined above and RQ is alkyl having 1 to 4 carbon atoms or aryl having 6 to 10 carbon atoms)], one compound having the formula (1) '& Also provided is a process for producing a compound having the formula (In), which comprises converting the compound to another compound having the formula (1)Y.

In step (a), the alkylating agent is typically a compound having the formula % or a leaving group such as alkyl- or arylsulfonyloxy. Alkylation reactions usually involve alkali metals (e.g. hydrogenation)
In the presence of a base such as potassium carbonate or an alkali metal carbonate, for example potassium carbonate, dimethylformamide maturation is carried out in a polar solvent such as dimethyl sulfoxide.

The reaction is typically carried out at non-extreme temperatures, usually between -209C and -1
It is carried out at 50°C, preferably in the range of 25°C to 50°C.

Alkylating agents can be prepared by or analogous to methods well known to those skilled in the art. For example, when A is the group NOR7, the alkylating agent can be prepared by the following reaction steps.

Step (1)) is carried out under conditions well known to those skilled in the art.

When the final product has the group A-NOR7, the compound 11 of formula (2) is typically prepared at non-extreme temperatures, suitably between -20°C and 150°C, preferably at temperature, in a polar solvent. ) Reacts with i2NOR7.

Compounds of formula @) can be prepared by ozonolysis of compounds having formula, and compounds of formula (IV) can be prepared by chlorination of compounds having formula (n)Y under conditions known in the art. It can be prepared by reacting with a delanyl halide such as delanyl. For example, KuWanO et al., Agr.
:LC, B111. Chem, , 198294
See 6.1715-1716.

Compounds having the formula UtU can also be prepared by hydrolysis of compounds having the formula.

Compounds having the formula (Vl''r) can also be prepared by standard methods from compounds having the formula (II) Y, where L is removed.Salts of compounds of formula (1) can be obtained in the form # by adding a suitable salt to a compound of formula (1).

The compounds of formula (1) are suitable for use against arthropods such as pests such as insects and mites, fungal pests such as molds harmful to crops, preserved agricultural products and wood, animal parasites and soil nematodes. It can be used to control or exterminate harmful organisms such as parasites. Accordingly, the present invention provides a method of administering to arthropods, fungal pests and/or parasites, or to their environment, an effective amount χ of a compound having the formula mv. /Also provides control or extermination f2 of parasitic worms. A method of controlling or exterminating an infestation of arthropods and/or parasites in animals (including humans), comprising administering an effective Qyt of a compound having 2m'Y, according to the present invention; and/or
or methods of controlling or exterminating arthropod and/or fungal infestations on plants (including trees) and/or stored products. The invention further relates to human and veterinary medicine, public health control and arthropod, fungal and/or
Alternatively, a compound having the formula (1) used in agriculture for controlling parasitic pests is also provided.

The term "control" means the present and future harmful effects of pests, including killing adults, larvae and eggs, inhibiting reproduction, repelling and/or overwhelming pests and other effects on behavior. includes.

The compounds of formula (1) can be used in the maintenance of fields, feed, plantations, greenhouses, orchards and vineyards, ornamental plants and hardened and forest trees, such as (corn, wheat, rice, millet, oats, barley, Cereals (such as kolya/), cotton, tobacco, vegetables and vegetables (such as beans, turnips, cassava, lettuce, onions, tomatoes and koshiyo), and salads (such as potatoes, sugar beets, peanuts, soybeans, rapeseed) ) Field crops, sugar #v.

pasture and fodder crops (such as purple horse palm), garden crops (such as tea, coffee, cocoa, banana, oil palm, coconut palm, im, spices), (kernel and rhizome fruits, citrus, Keelai fruit, avocado, man♂,
Orchard and forest crops such as olives and walnuts, ornamental plants in gardens, greenhouses and in gardens and parks, flowers and shrubs, forest trees (deciduous and evergreen) in forests, plantations and nurseries, and (evening primrose) This is extremely unnecessary for the protection of plants grown for industrial or pharmaceutical purposes.

The compound of formula (1) can be used to extract wood (standing, fallen, converted, preserved or architectural) from sawflies (e.g.
Urocerus) - or beetles (e.g. scolytids (5ccHytids), platibozides (plat
ypoaii8), lyctias,
Bostrytide (bostrychiaa), cerambycias (aerambycias), anopiids (a
It is also necessary to protect against attacks by nobiids).

The compound of formula (1) protects preserved products such as cereals, fruits, nuts, spices and tobacco, whole, ground or incorporated into products, from attack by moths, beetles and mites. used for.

natural or (e.g. carpet or textile strands)
Preserved animal products such as skin, hair, fur and feathers in transformed form are also protected from attack by moths and beetles, and preserved meat and fish are also protected from attack by beetles, mites and flies. Ru.

The compounds of formula (1) are useful in controlling organisms that are harmful to public health, such as dechypria and ants.

Compounds of formula (1) are harmful to humans and domestic animals, are persistent in spreading diseases and as vectors of common diseases, and are also important in the control of arthropods and parasites such as those mentioned above, and more specifically. Haha Ri'2 (ticks), Dani (mites)
), lice, fleas, gnats, bites, nuisance flies, mosquitoes and hemipteran control.

The compound of formula (1) can be prepared by applying the compound itself or by dipping, spraying, fumes, lacquers, foams, dusts, powders, aqueous suspensions, pastes, glues, creams, etc.
Shampoos, greases, flammable solids, vaporizing bodies (e.g. vaporizing mats), flammable coils, baits, dietary supplements, wettable powders, granules, creams, ointments, aerosols, emulsifiable concentrates, oil suspensions, Oil baths, overpressure packs, impregnated products (e.g. ear tags or calans, microcapsules, pour-on compositions)
It can be used for the above purpose in diluted form in a known manner, such as in the form of a formulation (formulation) or other oleaginous compositions well known to those skilled in the art. The spray liquid can be administered by hand, by means of a spray flume or arch, or by a device mounted on a vehicle or aircraft. animals and soil being processed;
Plants or other surfaces may be saturated with the spray liquid using high volume doses, or coated on different surfaces with the spray liquid using light or very low volume doses. The immersion solution is not administered by itself, but is diluted with water and the animal Z-immersed into a immersion bath containing immersion cleaning solution. Aqueous suspensions can be administered as well as sprays or dips. The dust can be applied by a powder applicator or, in the case of μ animals, may be formulated in a perforated bag attached to a tree or rubbing bale.

Pastes, shampoos and greases may be applied by hand or sprinkled onto the surface of an inert material so that the animal's body! a- The material may be transferred to the skin by rubbing. The spray composition is distributed over the animal's back as small volume units of liquid, such that all or most of the liquid is retained on the animal.

Although the compound of formula (11) can be prepared as a composition ready for use on animals, plants or surfaces, or as a composition requiring dilution for administration, both melon compositions Both consist of intimately mixing the compound of formula (1) & one or more carriers or diluents. The carrier may be liquid, solid or gaseous, or alternatively a mixture of these substances. The compound of formula (1) may contain between 0.025 and 90% depending on whether the composition requires further dilution.
It can be present at a solubility of 9% (weight/volume).

Dusts, powders and granules and other solid compositions are
The compound of formula (1) is combined with a suitable clay, kaolin, bentonite, attapulgide, adsorbent carbon black, talc, mica, silica, chalk, cast, tricalcium phosphate, powdered cork, magnesium silicate, a vegetable carrier, It consists of intimate mixing with a powdered solid inert carrier such as starch and diatomaceous earth. Such solid compositions are generally impregnated with a solid diluent with a solution of the compound of formula (1) in a volatile solvent, the solvent is evaporated and the product is ground to obtain a hand powder, if desired; If desired, the product is prepared by granulation, pressing or encapsulation.

Sprays of compounds of formula (1) can be prepared in the art from solutions in organic solvents (e.g. the solvents below) or from emulsifiable concentrates (also known as water-miscible oils) which can also be used for immersion. The concentrate may consist of a water emulsion (immersion cleaning solution or spray cleaning solution) prepared.
Preferably it consists of a mixture of the active ingredient with or without a solvent and 18 or more emulsifiers. The solvent μ can be present within wide limits, but preferably from O to 9 of the composition.
9.5 g/vol. and selected from kerosene, ketones, alcohols, xylenes, aromatic naphthas, water, mineral oils, aromatic and aliphatic esters and other solvents known in the formulation art. The concentration of the emulsifier can be varied over a wide range, preferably ranging from 6 to 25% ([f&/volume]), the emulsifier being a polyoxyalkylene/ester of alkylphenol and anhydrous hexitol. Non-ionic surfactants such as polyoxyethylene derivatives, sodium lauryl sulfate, fatty alcohol sulfates, sodium and calcium salts of 7h kylaryl sulfonic acids and alkyl sulfosuccinic acids, soaps, lecithin, hydrolyzed Anionic surfactants such as glue are advantageous.

Wettable powders consist of an inert solid carrier, one or more surfactants and optionally stabilizers and/or antioxidants.

Emulsifying properties [1] consist of an emulsifying agent and often an organic bath medium such as kerosene, ketones, alcohols, coals, xylenes, aromatic naphthas, and other detergents known in the art.

Wettable powders and emulsifiable #silks are usually 0.5-99
．． Contains 5kk% of active ingredient and is diluted with water, for example, before use.

The lacquer consists of a bath of active ingredient organic seedling medium with a resin and optionally a plasticizer.

The immersion cleaning solution can be used not only for emulsifying a-knitted fabrics, but also for wettable powders,
Soap-based dipping liquid and the compound in the formula dispersed and 1a! It can also be prepared from an aqueous suspension consisting of a thorough mixture of the above surfactants.

Aqueous suspensions of compounds of formula (1) consist of water suspending agents with suspending agents, stabilizers or other agents. Aqueous suspensions can also be formed from acid addition salts of compounds of formula (1). They may be administered as such, such as S preparations or baths, or in diluted droplet form in a known manner.

Wetting agents and/or solubilizing agents may also be present in the compositions of the invention, if suitable or desired.

Greases (or ointments) can be prepared from vegetable oils, synthetic esters of fatty acids or wool fat and an inert base such as soft paraffin. Preferably, the compound of formula (1) is uniformly distributed in the mixture in the form of a bath or suspension. Greases can also be made from emulsifiable concentrates by diluting them with an ointment base.

Pastes and shampoos are also semi-solid preparations and have the formula (
The compound of 1.) may be present as a homogeneous dispersion in a suitable base such as soft or liquid paraffin, or prepared from a non-greasy base and glycerin, viscous or a suitable soap. be able to. Since greases, shampoos and (-st) are usually administered without further dilution, they can be prepared using the appropriate proportions of formula (1) to mimic the treatment.
should contain the following compounds.

Aerosol sprays can be prepared as a simple bath of the active ingredient in an aerosol propellant and a co-proprietary medium such as halogenated alkanes, propane, butane, dimethyl ether and the swamp mediums respectively mentioned above. Spray compositions can be made as a bath or suspension of a compound of formula (1) in a liquid medium. Avian or mammalian hosts can also be prevented from infestation by mite ectoparasites by wearing suitably shaped and shaped plastic articles impregnated with the compound of formula (1). Such products include impregnated collars, tags, bands, sheets and strips that are suitably attached to appropriate areas of the body. Preference is given to the plastic material IRS, polyvinyl chloride (CPVC). impregnated bands, sheets or strips,
The trip can also be placed in a suitable location within an animal housing room or other suitable environment to control the ingress of pest agents into that environment.

The concentration of the compound of formula (1) to be administered to a location, such as an animal, house, other substrate or outdoor part, will depend on the compound selected, the treatment interval, the nature of the composition, the anticipated infestation. Although it varies depending on the characteristics of the position and the position, it is generally 0.001 to 20% (1 noble/capacity), preferably 0.
．． 01-10% of the compound should be present in the composition to be administered. The amount of compound deposited depends on the compound selected,
It varies according to the method of administration, the area of administration, the concentration of the compound in the composition to be administered, the factor by which the composition is diluted, and the nature of the composition, but generally 0.0001% to 0.0001%, except for undiluted compositions. It is in the range of 4%.

Undiluted compositions, such as spray compositions, typically contain 0.1
Administered at a concentration in the range of ~20.0 yen (k amount/h amount),
Preferably, it is administered at a fa degree of 0.61 to 10. The amount of compound administered to the preserved product generally ranges from 0.1 to
In the range of 20 ppm. The spatial spray contains 0.001 to 1 L9 of the compound of formula (1) per 1 g3 of treatment space.
can be administered to give an average initial concentration of .

The compounds of formula (1) are useful for the protection and treatment of plants, where effective insecticidal, acaricidal and fungicidal active ingredients are administered. The rate of application will vary depending on the compound selected, the nature of the composition, the mode of administration, the plant species, the density of the vegetation, and the anticipated infestation and other similar factors, but in general, suitable application rates for the crop are 0. 001-3 kg/Ha, preferably 0-01-11c9/Ha. Typical compositions used in agriculture are from 0.00 ml to 50% formula (
It is advantageous to have from 0.1 to 15 liters of a compound of formula (1).

Dust, grease, paste and aerosol compositions are generally administered randomly as described above and have a formula of A compound, preferably 0.001 to 20 units (1 unit/volume) of the compound can be used.

The compound of formula (11) is derived from the common houseplant z (Muaca
dom-estica) and the wood-destroying mold, Con1ophora puteana.
, Coriolua ('l'rametes)
), rust (areob)
Asldium pullulans) b and rot (Chaetomium globosum) were found to have activity. Furthermore, certain expressions (
The compound of 1) is Blattella germani
It is active against arthropods such as ca and Boophilus mlcroplus. Therefore, equation (1)
The compounds are useful for controlling arthropods and molds in the environment, which constitute pests, for example, in agriculture, livestock, public health care, and domestic use.

Insect-like pests include Coleoptera (e.g.
ium, Ceutorhynchus, Rhync
hophorus.

Hylotropee, (::08m0pO'1it
eEI XIJssorhoptrue, M811ge
thθB, Hypothenemus, Hylesin
us, Acalymma, Lema,
Psyllodes, 1eptinotars
a.

Gonocephalum X Agriotes,
Dermolepicia.

Heteronychus, phaedon, Tr.
ibolium.

5itophilus, Diabrotica
, AnthonOmu89 CpAnthrenu
s species), Hymenoptera (e.g. Ephest, ia.

Tinea, Mamestra, Eari
as, p8ctinophora.

□5trinia, Trichoplusia, p.
ieris, Laphygma.

Agrotis, Amathes S Wiseana
, Rr7POr7Za %piatra8a ,
Sporganthis, Cydia, Arc
hips, plutella, Chilo, He1i
othis, 5poaoptera'! r: Ia
, Tineola m), Diptera (e.g. Mue
ca.

AedeB, Anoph131e8, cu
lθX, GloEl day 1na.

Simulium X 3tomoxys, Haem
atobia X Tabanus.

) (hydrotaea, Lucilia,
(::hrysomia, Callitroga
.

Dermatobia
s, Hypoderma.

Hylemy: La, Atherigona,
ChlOrops, ph7tom7Za.

Ceratitis, liriom7Za and Mel
ophagus Wh), Phthirabtera (phthi)
raptera) (Malophaga.

e.g. pamalina ii, and Anoplur
a, e.g. Linognathus b and Haem
atopinus 73), early (e.g. Aphi
s,]3emisia, phoroaon.

Aenaolamia, gmpoasca,
Parkinaiel engineering a1 Pyrilla,
Aonidiella XCoccus, pseudo
coccus.

H610pelti13, LyguB,
Dy5dercus, 0K7Care
nu8, Nezara, Aleurodes,
Triatom, Rhodnl, us.

peylla, M7zuEl, M
egOura X Ph7110Xera.

Adelyes, Ni1oparvata, Nep
hrottix also ClmeX fi4), Orthoptera (e.g. Locusta).

Gr711u9, 5chistocerca f or Acheta], Dictyoptera (Dictyoptera)
tera) (e.g., 131attella,
Periplaneta or Blatta >n)
, Hymenoptera (e.g. Athalia, Cephus
, Atta.

LaEliuEi, +501enop81B or Monomorium a), Isoptera (Isopt
era) (e.g., Odontotermes and Reticulitermes), Siphonaptara (e.g., C”t
enocepha'1ides mata P, leX m
), Thysanura (e.g. Lepisma species), De/L/ Dermaptera
(e.g. Forficula australis) Puncoptera (ps.
ocoptera) (e.g. peripaocus
il ) and Thysanoptera (e.g. T
hripa tabaci).

Mite harmful offerings include mites such as Boophilus, us
, 0rnithodorus, Rh1picephal
us, AmblyOmma.

Hyalomma, lX0fLθs, Haema
physalia, Dermacentor and An
those of the genus ocentor, and mites and scabs, such as Acarua, 'petranychus.

paoroptes, 1Jotoeanes, Ba
rcoptas.

psorergate8, ChoriOpt, C8
, Eutrombicula.

pemoae:c, PILnOn7Chu8, Br
yobla and Er1ophyes Dermato
phagoidea, Tyrophagua and G.
There is lyayphagus.

Agriculture, Forestry, (9) Nematodes that attack plants and trees directly or by spreading bacterial, viral, mycoplasma, and fungal diseases that are important for agriculture include root knots.
J nematodes, such as MelOldogyne a (e.g.
M. incognita), cystocysts (e.g., T.
□1oboaera fi (for example, G, roetoc
hiensis ), )1eterodera M (
For example, H. avenae ), Radophulus
'4'll (e.g. R9aimilis), lesion nematodes, e.g. praty1enchus species (e.g.
P.

pratenai8), Belonolaimue
Maki (for example, B.

gracilia), Tyxenchulia m
(For example, T.

emipenetrans), Rot71ench
ulua species (e.g. Roreniformis),
Rotylenchus [(e.g. R6robus
tua),)(elicotylenchus leak(
For example, H6 multicinctus ), Hem
icyclophogra masses (e.g. H, gra
cilis), Criaonemolea iJC
For example, C6simC65i), Triahodor
ua species (for example, T.

primitiveus), dagger (CLagger
) nematodes, e.g.) (iphinema species (X, div
eraicaucLat, un ), Longiao
rue m (e.g. L, elongatus)
, Hopxolaimus wA (e.g. 11. c
oronatus), Aphelencholaea
ridge (e.g. A, ritZθIQIL-b081,
A, be8aeyi), stem and bulb nematodes, e.g. Ditylenchus fig (e.g., dip.
aaci).

Mold pests include wood destroying and crop molds, e.g.
Merulius lacrymans, POri
a placenta.

GIOelOph711um species, Corlolua (
'prametes)'ver810010r and 8tereum hirsutum, pucci,
n1areconalta, '[JrOm7C
+38 pha81Q11, '[Jatila
g.

maydlJ, Ti1letia caries
, Ustilago nuda.

1hizoatonia 5olani, Aaxomy
cetee, such as Chaetomium globo
sum, venturia 1naequal
ie.

3phaerotheca fuligi, nea
, podoephaeraleucotricha
, Erysiphe graminis, U
ncinulanecator
ra species, such as peuter.

m7ceteB, e.g. Aurθobasidium
pullulans, Fusarium culmo
rum, 5eptoria noiorum
.

Botrytia fabae, pi, ric
ularia oryzae.

Botrytia cinerae, Fuea
rium n1vale.

V8rti(!u/llium albo-atrum
and penicillium digitatum,
MastigomyOetes, e.g. Phyto
phthora MakiPlaamopara vitic
ola and Pythium ult4mum.

These compounds exhibit a biocidal and/or overwhelming effect on arthropods and can be used to control larval as well as adult pests.

Compounds of the invention may be combined with one or more other active ingredients, such as (
Insecticides, fungicides (such as trethroids, carbamates, lipid amides and organophosphates), fungicides, athelmentolcg and/or antimicrobial agents (e.g. European Patent Application No. 148.526) , page 6, line 62 to page 7, line 19, which is incorporated herein by reference), and attractants, repellents, and the like. Furthermore, the activity of the compounds of the invention may be influenced by synergists or potentiators, e.g., one class of oxidase inhibitors of synergists such as biperoid ptoxide or progyl 2-propynylphenylphosphonate; The dosage can be increased by adding a compound of the invention or a pyrethroid biocidal compound. When an oxidase inhibitor synergist is present in the formulas of the invention, the ratio of synergist to compound of formula (1) is in the range of 25:1 to 1:25;
An example is about 10:1.

Stabilizers to prevent chemical decomposition that may occur with the compounds of the invention include antioxidants such as (tropherol, butylated hydroxyanisole and butylated hydroxytoluene) and scavengers (such as epichlorohydrin). .

The following examples illustrate the advantages of the present invention in a non-limiting manner.

Engineering 8A (4E)-6-acetoxy-4-methyl-hex-4-
zsu1/'(0,8N 1mbromotrichlorometh/(
0.94 g) of dry dichloromethane (14rnt) i'
Cool to tHQY-20°C and add hexamethylphosphorus triamide (1.6 g) to dichloromethane (10
M) 16g'1 drop was added and stirred. After 15 minutes, water and hexane were added to separate the bath liquid. Organic bath liquid Y
! Washed with hydrochloric acid, water, brine, dried and evaporated.

The crude product was column chromatographed on silica,
Numata was mixed with 1:1 ether:hexano. product (, 25
0+19) is δ1.8 <, e, 3 H, CH
,,), 2.0cs, 3H*COCH3), 2.2
(me 4 Hp CH2CH2), 4.5(
”= 2 f(, NCH2-8Hz), 5-2
(to 1 H.

-cH*8H2), 5.6 (t# I H, -
C1l, 6 Hz) with n, m, r, peaks? I had it.

The above ester (2501n) in methanol (20+M)
9) and anhydrous potassium carbonate (0.2 g) The mixture was stirred in a Y-room for 4 hours and evaporated to dryness. Add water and ether and bath g
Y: Separated. After washing with ether/L-salt saline, drying and evaporation, the product (150 m9) v? 1y
:.

n1m, r, peak (δ): 1.6 (B, 3
H, CH3), 2-2 (me4H-CHzCH
z), 4.0 (d, 2 EI.

NCH2# 8 H2), 5.6(” + I H
p -CHe 8H7), 5-6 (" p I
He-CH-6Hz).

Anhydrous lithium chloride (36~)'fJf in dimethylformamide (4:ILt): While adding the above alcohol (
150+19) and lutidine (99■)'? : Stirred. While cooling the mixture to 0 °C, mesyl chloride (77
1 μl) and continued stirring at this temperature overnight. Water and ether? Additionally, 7 ethereal solutions were separated, washed with a saturated copper nitrate bath, brine, dried, and evaporated to yield the product (,1501A9)y1'.

n0m, r-(b>: 1.s Ca, 3H,
cl(,), 2.1(m, 4H, CH2CH2
), 4.0 ((1,2H,NO)!,.

8Hz), 5.4 Ct, III, -CH,
8H2), 5.6 (t, I H, -Cl-1,6
Hz).

Step B 2-Methylbenzimidazole is alkylated with 6-ethylenedioxy-1-promo-6-methylhex-2(E)-ene as in Step A to give the product ? 11
child.

n, to, r, peak (δ): LS C8,3)1
．． CH5), 2, LI (11,4) (I C)
12 fields (2), 2.4 (s, 3H.

N-CCH3), 3.8 (m, 4H, 0C
R2(J(20), 4.6 (d,, 2 H,N
CH218H2), 5.2 (t.

IH*-CHe 8H2), 7.0-7.
6 (m, 4)I.

aromatic).

The above acetal (100D), which had been disintegrated in edone acetate (1011U), was shaken for 15 minutes with concentrated hydrochloric acid (3 hours). 2N sodium hydroxide was added, and the separated organic layer was diluted with water. Washing with brine, drying and evaporation gave the aldehyde (431 ml).

n, m, r, r-ri (δ): 1-8 (Be 3
H*Me), 2.0 CIl+, 4H,C
H2CH2), 2.6(,8,3[(.

N-cMe), 4.6 (li, 2H, NC
H2,3H2), 5, C1(t, I H, -CH,
8H2), 7.1-7.8 (me 4 H* aromatic fit),
9.4 (+-, 1H, C'H0°2H2).

Step C 1-geranyl-2-methylbenzimida doorol (1,
0,! 9) methanol (100mj) solution at -70°
C. and selectively ozonated.

Dimethyl sulfide (21114) Fa' was added and the bath solution was stirred at room temperature overnight. The solvent was removed and water and ethyl acetate were added. The organic solution was separated, washed with brine, dried and evaporated to give the aldehyde (200m9).

Example 1 Midazole 2-Methylbenzimidazole (100119) in dry dimethylformamide (4d) was suspended in dimethylformamide (1rnE) of sodium hydride (301n 9.60% oil dispersion) stirred at 0 °C under nitrogen. Added to the suspension. After 0.5 h, 1.7.7-dolichloro-3-methylhept-2E,6 in dimethylformamide (1-)
-Diene (150~) (from Example A) was added and the mixture was left at room temperature overnight. Ice and water were added and the mixture was extracted with ethyl acetate. The organic phase was washed with brine, dried and the solvent removed in ``vacuo''. Chromatography on silica and bathing with ethyl acetate gave the product (52 da).

nD=1.5446, n, m, r, peak (') ”
1.8 (s.

3 H # Me), 2-2 (m # 4 H, CH
2CH2), 2.5(s # 3H*NCH3), 4.
6 (a, 2H, NCR2゜J = 8 Hz),
5.2 (t, , IB, =CH, 8Hz), 5.6
(z, I H=CH, 6Hz L 7.0~
7.7 (m.

4H, aromatic).

Example 2 A solution of the aldehyde (200 ~) from Sol Step C in tetrahydrofuran (15jfiA) was treated sequentially with methoxylamine hydrochloride (200 μl), lysine (200 μl) and water (4 times). The bath was heated at reflux for 1 hour, cooled and evaporated. Chromatography (on silica) eluting with ethyl acetate gave the product (52 mg
) f: Obtained.

Example 3 Sol (1) (If) (1)
(IV) Oxime (n) Tetrahydrofuran (100 ffli dibalyzed 6-acetoxy-4-methyl-trans-4-hexanal (
The mixture was stirred while adding a solution of hydroxylamine hydrochloride (4 g) in water (251d) and bilicin (7μ). The alpha compound was heated at reflux for 1 hour, cooled, and water and ether were added.

The oxime (f
l) (5,1F) f: Obtained.

n, +n, r, t-ri (J): 1.8 (s,
3H, COMe), 2.1(a, 3H, Ms), 2.
4 (m, 4 H.

cI (2cI(2), 4.7 (d, 2H, CH
2O), 5.4 (c.

1H, = CI4), 6 and 7.4 (t, 1
)1, HC=N).

Oxime (seal) Anhydrous potassium carbonate (5y) and iodomethane (2,3
9) of oxime (11) (2,9) in dry ethanol (
60 red) solution and the mixture was heated at reflux temperature for 3 hours. The solvent was removed in vacuo and ether and water were added. The 4a-containing solution was evaporated, washed with water and brine, dried, and concentrated to yield oxime (1) (1,269>).

n, m, r, e-ri (#): 1.8 (s, 3
H, Me), 2.3 (m, 4 H, CH2CJ(
2), 3.9(s, 3H.

OMa), 4.2 (d, 2H, CH2O),
5.5 (t, .

1H,=CH), 6.8 and 7.4 (c, I
H, He=N).

A number of similar oximes (1) were prepared, except that 1Hn, m, r, differed as follows.

R4 = benzyl, 4.6 and 5.0 (s, 2H.

CH2Ph), 7.1 (s, 5H, aromatic).

B4 = Zoropa N-Gil, 1.3 (+n, IH, aCH),
4.7 (d j 2 H, Cl2C8).

R4 = allyl, 4.6 and 5.3 (d, 2H
, C) (2C'=), 5.2 (m, 2H, CH2
=).

R'=n-butyl, 1.0-2.0 (m, 7H
.

OH□CH2CH3), 4.0 and 4.1 (m, 2H
.

CH2O).

R4=ethyl, 1.3 (t, 3H, 0H2C'H
3), 4.1 (q, 2H, CH2CH3).

Chloride (IV) R' = Me0 Lithium chloride (3701n9) is converted into oxime (gate) (1,
2g) and lutidine (0,85&) in a dimethylformamide (1011u) bath solution. The mixture was cooled to 0°C and methylsulfonyl chloride (0.9g) was added. After standing overnight at -10°C, water and ether were added to separate the ether m solution, washed with water and saturated brine, dried and concentrated to obtain the product (0,59). .

n, m, r, beak (J)' 1.8 (s, 3
H, Me), 2.3 (m, 4'H, CH2C
H2), 3.9(s, 3H.

OMe), 4.0 (d, 2H, CH2), 5.
5 (Z.

IH,=CH), 6.8 and 7.4 (c, IH,
HC=N).

1-(2(E)-6-Medoxyimino-3-methylhex-2-enyl)-2-methylbenzimidazole 2-methylbenzimidazole (200~) All Examples 4
The product was alkylated with chloride (IV) (300 μ) as described in 61.9 (s, 3H, Me
), 2.3 (m, 4H, CH2CH2)2.6
(a, 3H, N=C-Ms), 6.75 and 3
．． 85 (s, 3H, OMe), 5.2 (t#2H.

CH2-N), 6.5 (Z, IH, CH=N)
, 7.2-7=6 (m, 4H, aromatic) had a peak.

``A number of analogs were prepared that were similar except that Hn, rn, r, differed in the following respects.

R = benzyl, 5.4 (s, 2H, CH2Ph
).

Professional! -2-ynyloxy]hex-2-enyl]benzimidazole, R=nibrobagil 1.3 (m, iH, 5CH), 4.6
(d, 21 (, Tomo 20).

R=n-butyl, 1.0-2.0 (m, 7 H, c
H2CI(2CH3), 4.1 (m, 2H, 0
CH2).

Two soils R = ethyl, 1.0 and 1.1 (z, 3H.

42su3), 3.9 and 4-0 (Q, 2H.

Tomo 2CH3).

Example 4 N-Butyllithium ate (1,6M in hexane) (5,1
d) in dry tetrahydrofuran (30 m) of diisoprobylamine (0,67 g) stirred at 0 °C under nitrogen.
Added to bath solution. The solution was cooled to -78°C and diluted with triethylphosphonoacetate (1,81 in tetrahydrofuran).
' was added. After stirring for a further 40 minutes, 5-methylhex-4-enal (1.8 g) in tetrahydrone (
5m) solution was added and the solution was allowed to warm to room temperature overnight. Ether and water were added, the ethereal solution was separated, washed with dilute hydrochloric acid, saturated sodium carbonate solution and brine, dried over sodium sulfate and evaporated to give the product (2,1 &
) was obtained.

np "" 1.4610, infrared spectrum (liquid film): 1730. L-1゜The above ester (1,
0g) t-5°C and a solution of sodium bis(2-methoxyethoxy)-aluminum hydride (0.8m) in benzene (10ffin) was added over 15 minutes.b
The solution was allowed to warm to room temperature overnight and saturated ammonium chloride solution was added. The organic phase was separated, washed with brine, dried over sodium sulfate and evaporated to give the product (0,79)
I got f.

HD=i, 4770, infrared spectrum (liquid film): 3000-3500 cz-1°C) Ia on 7-methylocto-2,6-genyl bromide
A solution of flucol (0.7 g) in diethyl ether is
It was cooled to 0.degree. C. and treated with bilicin (100111e) and phosphorus tribromide (200 .mu.l). 711 compound till 6 o'clock
After he had fully recovered, the temperature was brought to room temperature and ice was added. The ether solution was separated, washed with water, saturated sodium monocarbonate, brine, dried over sulfuric acid (IJ) and evaporated to give an oily product (0.79).

nD = 1.4978, nmr peak (J): 1.0 (m, 6H, 2x
Me), 2.1 (m, 4H, CH2CH2)
, 4.0 (m, 2 f(.

NC'H2), 5.1 (m, IH, =CH), 5.7
(m.

2 H, C) (=CH).

2-Methylbenzenimidazole was alkylated with 7-metelooct-2,6-genyl bromide as in Example 1 to give an oil.

nD=1.5550, nmr peak<a): 1.5 and 1.6(s, 6
H.

'l xMe), 2.0 (m, 4H, CH2
0H2), 2.5 (s e 3 H* = NMe),
2.5 (rn, 2H, NCH2,), -5,0
(m, IH, = CI-T), 5.4 (m,
2H, CH=CH), 7.1 (m, 4H, aromatic).

Example 5 (imidazol-1-yl)hex-4-enal] 7cety7t, (9Qau) chloride? , (4Ee)-4-
Added to a stirred aqueous (2 ml) solution of methyl-6-(2-methylbenzimidazol-1-yl)hex-4-enaloxime (150~) and sodium hydride (52~). After stirring overnight at room temperature, ethyl acetate was added. Separate the organic solution, wash with water, brine, dry over *# sodium cum and evaporate "vacuum" to give the product (50mp)
I got it.

nn1r beak (J): 1.9 (s, 3) T, Me),
2.1 and 2.2 (a, 5H,'l xcO
Me), 2.4 (m.

4 H, CH2CH2), 2.6 (s, 3H, =
NMe), 4.7 (m, 2H, NCH2),
5.2 (m, IH, = -2-one) A solution of the aldehyde (200~) from c and acetylmethylenetriphenylphosphonine (530) dissolved in benzene (20 ml) was heated at reflux temperature for 6 Heated for an hour. After cooling, water and ether were added and the mixture was separated. The ether solution was washed with brine, dried and evaporated.

Chromatography (silica) and bathing with 1:10 hexane:ethyl acetate gave the product (70m9).

nmr beak (j): 8 (s, 3H, Me
), 2.1 (s.

3 H, COMe), 2.2 (m, 4 H, C
H2CH2), 2.4 (s, 3H, N=CMe
), 4.6 (m, 2H.

NCH2), 5.2 (m, IH, =CH), 6.0 (
d.

I H, =CH, 16Hz), 6.6 (m, I
H, =CH), 7.2 (m, 4H, aromatic)
.

The following compounds were prepared in the same manner as above by reacting the aldehyde from Example C with the appropriate Itteitz reagent.

(6E)-6-mete-8-(2-methylbenzimidazol-1-yl), -1-phenylocta nmr peak (J): , 8(s, 3H,Me), 2.6(m
a4H*CH2CH2), 2.5(S,
3H, N'=CMe), 4.6 (m,
2H, NCH2), 5.2 (I]l.

1H,=C)J), 6.8-8.0 (m, 11
H, aromatic 10H=CHO).

Ethyl = 6-methyl-8-(2-methylbenzimidazol-1-yl)octa-2,6-genoate nmr peak (a): 1.2 (s, 3H, C
H2Me.

7 Hz), 1.8(s, 3H, Me), 2.
3 (m.

4 H, CH2CH2), 2.4 (s, 3H, N
=CMe), 4.2 ((1, 2H, 0CH2, 7Hz
), 4.6 (m.

2H, NCH2), 5.2 (m, IHj=CH), 7
．． 1-7.9 (m, 6H, aromatic+CH=CHO).

-2,6-genyl)benzimidazole nD: 1.5
085, nmr peak (J): 1.4 (m, 3H,
=CL'vie), 1.7 (s, 3H, Me), 2.
0 (m, 4 H.

CH2CH2), 2.4 (s, 3H, N=CM
e), 4.4 (m, 2H, NCH2), 5.1
(m, 3H, =CH), 7.2 (m, 4
H, aromatic).

Female Musca domestica without bioactive anesthesia
The activity of the compounds of the invention against (strain WRL) was demonstrated by topically administering a solution of the test compound in Seronlube to the test insect. Survival rates were assessed after 10 minutes, 1 hour, 24 hours and 48 hours.

Compounds with DL5o<10μy/fly include 1-[
(2E)-6-Medoxyimino-3-methylhex-2
-enyl]-2-methylbenzimidazole, (2E)-2-methyl-1-(3-methylocta-2,
6-genyl) penzimidazole.

B. Anti-fungal test The anti-fungal activity of the compounds of the present invention was measured using a soft agar screen. Concentration-dependent inhibition of hyphal growth of Coriolus versicolor.

Con1phora puzena, Aureob
asidium pullulans and Chaet
, omium globosum was measured.

The following had IC5o<30 ppm.

1-[3-methylhepta-2,6-dienyl-2-methylbenzimidazole, 1-[hepta-2,6-dienyl]-2-methylbenzimidazole, (2F)-2-methyl-1-(6-methylocta -2,
6-genyl)benzimidazole, 2-methyl-1-
[(2E)-3-methyl-6-benzyloxyhex-
2-enyl]benzimidazole, 1-[(2E)-7,7-dichloro-3-methylhepta-2,6-enylcy2-methylbenzimidazole.

Toxicity to C0 mammals When 1-(2E)-6-medoximinor-3-methylhex-2-uni-2-methylbenzimidazole is orally administered to mice (Charles River CD 1 ), the LD5o is approximately 200 ~ .

Formula (ingredients, expressed as 90 M amount/weight 17) 1,
Emulsifiable concentrate compound of formula (1) io, o.

Rzhylan K E O20,00 Xylene 67.50 Butylated Hydroxyanisole 2.50100.0
0 2, wettable powder Compound of formula (1) 25.00 Attapulgide 69.50 Sodium isoprobenzene sulfonate 0.50 Sodium salt of naphthalene sulfonic acid 2.50 Butylated hydroxytoluene 2.50io
o, o.

3. Compound of dust formula (1) 0.50 Butylated hydroxytoluene 0.10 Talc
99.40100.00 4. Compound of bait formula (1) 2.5 Resin
5. .

Butylated Hydroxyanisole 0.5 Highly Aromatic White Strit 92.0100.0 [
] 5. Compound of lacquer formula (1) 0.30 Resin 5.0 Butylated hydroxyanisole 0.5 Highly aromatic white
Sugirit 92.0ioo, o.

6. Aerosol compound of formula (1) 0.60 Butylated hydroxyanisole 0.101.1
．． 1-) Lichloroethane 4.00 Odorless Kerosene 15.60 Arctoy
(Arczon) 11/12.50:50 mixture 80
．． 00 ioo, o.

Z Compound of spray formula (1) 0.1 Butylated hydroxyanisole 0.1 Xylene
10.0 Odorless Crocin
89.8ioo, o.

8. Compound of force spray formula (1) 0.1 Butoxy t-peronyl 0.5 Butylated hydroxyanisole 0.1 Xylene
10.1 Odorless Kewashino
89.2100.00

Claims (12)

[Claims] (1) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) [In the formula, R^1 is methyl optionally substituted with chlorine or one or two fluorine atoms, and R^2^ a~
R^2^d are the same or different and are hydrogen, chlorine, bromine, fluorine, alkyl having 1 to 4 carbon atoms optionally substituted by 1 or 2 fluorine or chlorine atoms,
By alkoxy having 1 to 4 carbon atoms, acyl having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, nitro, cyano, alkyl having 1 to 4 carbon atoms optionally substituted amino or 1
Alkanoyl with ~4 carbon atoms, R^3
is hydrogen or alkyl having 1 to 4 carbon atoms, A is the group X-Y-R^4 or the group CR^5R^6, where X is nitrogen, CH or C(R^7) (however,
R^7 is alkyl having 1 to 6 carbon atoms)
and Y is oxygen, sulfur, or the group NR^8 (however, R^
8 is hydrocarbyl having 1 to 8 carbon atoms) and R^4 is acyl having 1 to 4 carbon atoms or alkyl having 1 to 4 carbon atoms, R^4 is hydrocarbyl having 1 to 4 carbon atoms, alkoxy having atoms, acyl having 1 to 4 carbon atoms or hydrocarbyl having 1 to 10 carbon atoms optionally substituted by halogen, or when X is nitrogen, R^4 can also be hydrogen; Yes, R^5 is hydrogen, chlorine, bromine, fluorine, C_1_~_4 alkyl,
C_1_-_8 is selected from alkoxycarbonyl, alkenyl having 1 to 4 carbon atoms and acyl having 1 to 8 carbon atoms, R^6 being hydrogen, chlorine, bromine,
fluorine and alkyl having 1 to 4 carbon atoms] or acid addition salts thereof, except for 1-geranyl-2-methylbenzimidazole. (2) A compound having the formula (I) according to claim 1, wherein A is NOR^8 (wherein R^8 is alkyl having 1 to 4 carbon atoms). (3) A compound having the formula (I) according to claim 2, wherein R^8 is hydrogen or methyl. (4) Claims 1 to 3 in which R^3 is methyl
A compound having the formula (I) according to any one of paragraphs. (5) The formula according to any one of claims 1 to 4, wherein one or two of R^2^a to R^2^d are selected from nitro, methyl, methoxy and chlorine ( I). (6) 1-[2(E)-7,7-dichloro-3-methylhepta-2,6-dienyl]-2-methylbenzimidazole, 1-[2(E)-6-methoxyimino-3-methylhexa -2-enyl]-2-methylbenzimidazole, (6E)-6-methyl-8-(2-methylbenzimidazol-1-yl)-1-phenylocta-2,6-dien-1-one, 1- [3-Methylhepta-2,6-dienyl]-2-methylbenzimidazole, 1-[hepta-2,6-dienyl]-2-methylbenzimidazole, (2E)-2-methyl-1-(3-methylocta -2,
6-dienyl)benzimidazole and 2-methyl-1-[(2E)-3-methyl-6-benzyloxyiminohex-2-enyl]benzimidazole. (
I). (7) A composition for controlling pests, which comprises mixing a compound having the formula (I) according to any one of claims 1 to 6 with a carrier acceptable for pest control agents. . (8) A compound having the formula (I) according to any one of claims 1 to 6 for controlling pests such as insects, mites, or fungi. (9) Control of insect pests, comprising applying an effective amount of a compound having the formula (I) according to any one of claims 1 to 6 to the insects or to a place near the insects. Or extermination method. (10) Control of mite pests, comprising applying an effective amount of a compound having the formula (I) according to any one of claims 1 to 6 to mites or to a place near the mites. Or extermination method. (11) A method for controlling or exterminating fungal pests, which comprises applying to fungi an effective amount of a compound having the formula (I) according to any one of claims 1 to 6. (12) A method for producing a compound having formula (I), comprising:
(a) Formula ▲ Numerical formula, chemical formula, table, etc. ▼ (II) (In the formula, R^1 is as defined in claim 1, and R^2 is as defined in claim 1 Definition of R^2^
a to R^2^d), the group CH_2
(b) When A is NOR^7 or CR^5R^6, the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ After reacting the compound having formula (III) with a suitable hydroxylamine or Uitteg reagent, one compound having formula (I) can optionally be reacted with another compound having formula (I). The above manufacturing method, which comprises converting the compound into a compound.