JPS61167648A - Cyclopropane-containing tertiary amine compound, manufactureand fungicidal composition - 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] Containing tertiary amine compound. The present invention relates to a method for constructing such a bed, a fungicidal composition containing the same, and a method for using the same to exterminate fungal infections, particularly of plants.

According to the present invention, the following formula (■): In formula C, R', R2.几3, R4, R5 and R6 each represent a hydrogen atom, an alkyl group containing ~g carbon atoms, or a halogen atom, and R7 and R8 each represent a hydrogen atom or an alkyl group containing a Buddhist monk carbon atom. represent a group or together form a ring which may contain additional heteroatoms; Aryloxy group or group: 1.

(In the formula, 几9, 几10 and R are alkyl, alkenyl,
Alkynyl, cycloalkyl or aryl group)
Tertiary amine compounds and stereoisomers and acid addition salts thereof are provided.

Said compounds have fungicidal activity.

The compounds of the invention are generally obtained as mixtures of geometrically shaped isomers. However, these and other mixtures of optical isomers can be dispersed into individual isomers by methods known in the art, and such isomers form part of this invention.

When R7 and R8 taken together with the adjacent N-atom represent a heterocyclic ring, this is for example piperidine, morpholyl/
, thiomorpholine, pyrrolidine or piperazine rings, any of these rings may carry one or more substituents such as 01-4 alkyl groups or 7-enyl groups or hydroxyalkyl groups. .

Especially when the nickname for X and Y is an alkyl group, R
Also for 1-R8 and R9-R11, alkyl and alkoxy groups are straight-chain or branched alkyl groups having /~ carbon atoms (for X and Y and /~ h carbon atoms (for ~R)) and alkoxy groups; examples include methyl, ethyl, propyl (n- or isopropyl) and butyl (n-, see-, iso-
or t-butyl] and the corresponding alkoxy group. The cycloalkyl group for X and YK can be a cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl group.

The halogen atoms which R to B and X and Y may represent may be fluorine, chlorine or bromine.

For X and YK, alkenyl and alkynyl groups can contain - ~ carbon atoms, and ⇠? , R10 and RIIK
Thus, alkenyl and alkynyl groups can contain 2 to 3 carbon atoms.

Examples of these when X and Y are 7-aryl, a2-alkyl, aryloxy or aralkoxy groups are 7-aryl, benzyl, phenoxy and benzyloxy groups. These rings may contain the following substituents, halogen (e.g. fluorine, chlorine or odor l/g), 01-6 alkyl [e.g. methyl, ethyl, propyl (n- or isopropyl and butyl)
-+ 5ec-, ia- or t-butyl tLo, ~6
Alkoxy (e.g. methoxy, ethoxy, !ropoxy and butoxy containing halo 01-6-furkoxy (e.g. trifluoromethoxy) may have alkyl (e.g. trifluoromethyl), nidotetra, phenyl and phenoxy groups The phenyl ring may thus have no substituents or ring substituents as described above. preferable,.

The acid addition salts mentioned above are salts with inorganic acids or organic acids such as hydrochloric acid,
Six salts are obtained with nitric acid, sulfuric acid, acetic acid, gutluene-sulfonic acid or oxalic acid.

According to another gist, the present invention provides the following formula (IJ: (■) [In the formula, R1, R2, R3, R4, R5 and R6 may be the same or different, and contain a hydrogen atom and 1-3 carbon atoms. R7 and R8 may be the same or different and represent a hydrogen atom or an alkyl group containing 7 to 7 carbon atoms; or together as an additional heteroatom; forming a ring which can contain oxygen, nitrogen or sulfur and optionally have substituents; alkyl radicals containing from 3 to 6 carbon atoms, cycloalkyl radicals containing from 3 to 6 carbon atoms, alkenyl or alkynyl radicals each containing 3 carbon atoms, phenyl radicals, benzyl radicals, alkoxy radicals containing from 7 to 6 carbon atoms group, phenoxy group.

Benzyloxy group or group: 11° (wherein R9, R10 and 几 may be the same or different and are an alkyl group containing up to 7 carbon atoms.

tertiary amine compounds and stereoisomers thereof, each representing an alkenyl or alkynyl group containing ~μ carbon atoms, 3~representing a cycloalkyl group or phenyl group containing ~μ carbon atoms] and stereoisomers thereof and acid addition salts. .

According to another summary, the present invention has the following formula (I):! [In the formula, R1 and R,' are hydrogen,... rogene or C1-4
is an alkyl group; R3 and R4 are hydrogen; R5 and R6 are hydrogen or C alkyl groups; p: R7 and R
8 is a C4-41-4 alkyl group or together with adjacent N-atoms 0
1-4 alkyl, phenyl or hydroxymethyl group forming a morpholine, thiomorpholine or piperazine ring which may have a substituent; X and Y are hydrogen, halogen, 01-4 alkyl, 01-4 alkoxy, Phenyl, phenoxy, benzyl.

The present invention provides a tertiary amine compound having the formula: 119.R10 and R11 are 01-4 alkyl groups, and stereoisomers and acid addition salts thereof.

According to another gist, the present invention provides the following formula (I): (in the formula, ratio 1
and R2 are hydrogen, methyl or chlorine: FL5 and hydrogen or methyl; R7 and R8 are piperidine, 3. ! -dimethylpiperidine, morpholine, 6-dimethylmorpholine, diethylamino, phenylpipericine, 3-hydroxymethylbiveridine, thiomorpholine, piperazine or derphenylpiperazine; X and Y are 3 of the 7 enyl ring or G-position, one of which is hydrogen or C4
-4 alkyl group and the other is hydrogen, 0 alkyl, C1-4 alkoxy, chlorine, bromine.

1-4 phenyl, phenoxy, benzyl, be/zyloxy or C4-4 trialkylsilyl group) and stereoisomers and acid addition salts thereof.

Although the invention further provides certain compounds and stereoisomers and acid addition salts thereof as set forth in Table r and Examples 1-6 below, the invention particularly provides compounds having the following structural formula: The compound conforms to the above formula (1) K. The 'Hnmr (nuclear magnetic resonance) chemical shifts of certain portions of these structures are recorded to identify various compounds.

*Number of protons in the a-piperidine ring per 9 elements + Number of protons in the a-morpholine ring per oxygen atom Formula (■) (In the formula, R1 to R6 are hydrogen, and Ar
1082 tit) of a compound of lance
Onmr chemical Schiff) fl is given in the table below.

It is entirely intended to place the aryl group on the left-hand side of the cyclopropane ring for J which is 10H2- since both are H: ie they are in trans position with respect to each other.

In the following formula: In Y (in the formula [4', B2, R', FL',
as, B6, 1%, 7, 88, X and Y are as above. In the absence of a solvent, the following formula (I
I): ■ c formula 1. R2, R3, a', R5, R6, x and Y
is as described above, and 2 is a leaving group such as chlorine, bromine, mesylate or tosylate.
): L7 (wherein R7 and R8 are as described above) can be produced by treatment with a compound of formula 1n): 4'*fL2sEL'*tL'*K"tLL
6t. or by treatment with metal chloride in pyridine (or triethylamine) when 2 is a mesylate or tosyl chloride in pyridine (or triethylamine) when 2 is a tosylate. Can be prepared.

Alcohols of the above formula (Ili/) in which t3 and 4 are hydrogen can be prepared in a convenient solvent such as diethyl ether or tetrahydrofuran by formula (■): (wherein [(', E12., s, FL',
n can be prepared by treating the esters of X and Yd (Mtl<, and L is an alkyl group) with a reducing agent (usually lithium aluminum hydride).

Alcohols of the formula (F/l, in which R5 and R4 are alkyl groups) can be prepared by adding an ester of the formula (Vl) to an excess of alkylmagnetic acid or an excess of an alkyl group in a convenient agent such as diethyl ether or tetrahydrofuran. It can be improved by treatment with lithium.

A cinnamate ester of the formula (V), in which L, &5 and R6, VllJ: can be prepared by reacting with a phosphorane of Rho (wherein Rhu and R2 are as described above).

Alternatively, esters of formula (■) above (where R5 is hydrogen) can be prepared as follows: : Y (wherein R1, R2, 86, X and Y are as described above) can be prepared by t-addition of ethyldiazoacetate to the olefin.

The compound of the above formula (1) (wherein R3 and R4 are hydrogen) is prepared by f7' (in a convenient solvent such as diethyl ether or tetrahydrofuran) of the following formula (■): ('& in &'
, Rz, R5,8,6, a', aa, X and Y are as described above] by treating with a reducing agent (usually lithium aluminum hydride).

The amide of the above formula (IXJ is an acid chloride of the following formula oO: (wherein B1, EL2, BS, )L6, K and Y are T as described above) in a modest solvent such as diethyl ether or tetrahydrofuran. The following formula (Ul)
It can be prepared by reacting with a similar amine.

The acid chloride of the formula ω can be prepared in a convenient solvent such as hexane or dichloromethane by the following formula (koma: (where t'L'
, Rz, R5, R', X and Y can be prepared as described above by reacting certain J acids with conventional chlorinating agents such as thionyl chloride or oxalyl chloride.

The acid of formula (XI) can be prepared by hydrolyzing the ester of formula (9) in a conventional manner using sodium or potassium hydroxide in a methanol/water solution at room temperature.

Compounds of the above formula (■] (where al and R2 are halogens) can be prepared by adding a dihalocarbene in a convenient solvent such as chloroform or dichloromethane to the following formula (
xll): (wherein 5, g4, BS, 6. X and Y are usually all made from substituted allyl alcohols as described above.

Compounds of the above formulas (at), (VIIIJ and (shaku)) are described in the literature and can be prepared by standard methods.

The salt of the compound of formula (I) can be prepared by a known method.
) from the compound! ! ! I can escape.

The compounds, salts and metal complexes of the invention are effective fungicides, particularly against the following diseases: and other rusts and other host plants, such as coffee.

Rust of linoleum, vegetables and ornamental plants, other powdery mildews of barley and host plants such as gourd and other soybeans (Oercospora), tomato, yam, etc.
, grapes and other host plants. Some of the compounds of the invention also show broad spectrum activity against fungi in vitro 72
-6 These compounds are effective against various diseases of fruit trees after harvesting [e.g., orange green mold (Penicillum di
Some of the compounds of the present invention have been used to treat some of the common cutworms Fusarium spp, Fusarium spp.
“Kamahaften disease 8eptoria spp.

Ti1letia spp (i.e. wheat smut, a disease caused by smut), υstilag
o sppvHe1mi+shos orium sp
p, and Pseudocereco 5pore-order a
herpotrichoides% cotton silk disease (
It is effective as a seed dressing against Oorticium aasakii (Rhizoctonia solani) and rice sheath blight (Oorticium aasakii).

The compounds of the present invention can move apically in plant tissues from below in an apical direction. Additionally, the compounds of the present invention may be sufficiently volatile to be effective in the gas phase against fungi on plants.

The compounds of this invention may also be useful as industrial (as opposed to agricultural) fungicide agents, such as in the prevention of mold attack on wood, hides, leather, and especially paint films.

Although the compounds of the present invention can be used as is for fungicidal purposes,
For such uses, it is best to formulate it into a composition. That is, the present invention also provides a mold composition comprising a compound of general formula <i> as described above, or a salt of garlic, a goldfish complex salt, an ether or an ester, and optionally a carrier or a diluent. be.

The present invention also includes compounds such as those mentioned above or salts of garlic.

The present invention provides a method for exterminating molds, which comprises applying a metal complex salt, ether or ester to one gram of a plant or to the site of a second gerbil.

The compounds, salts, gold 114@salts, ethers and esters of the invention can be applied in a number of ways, for example directly to the leaves of plants in the form of formulations or in non-formulation,
Power/May be applied to trees and trees, seeds or other medium in which plants, kappa or trees are growing or intended to be planted;
Alternatively, the compounds, salts, metal complexes, ethers and esters can be sprayed, dispensed or applied as cream or paste preparations, or the compounds, salts, metal complexes, ethers and esters It can be applied as a full vapor and as a slow release fine granule. It can be applied to any part of the plant, kappa or tree, eg leaves, stems.

It can be applied to the branches or roots, or it can be applied to the soil surrounding the roots, or it can be applied to the seeds before they are sown; It can be applied to plants or hydroponic systems. The compounds of the invention can also be injected into plants or trees and can also be sprayed onto plants using electric spray technology.

The term "plant" as used herein includes seedlings, kappa and trees. Furthermore, the fungicidal method of the present invention includes preventive treatment, preventive protection treatment, preventive treatment, and eradication and eradication treatment.

The compounds of the invention are preferably used in the form of compositions for horticultural and horticultural purposes. (It depends on the type of composition used in the case, and the purpose of the special electricity encountered.

The composition of the present invention comprises an active ingredient and a solid diluent or carrier such as kaolin, bentonite, diatomaceous earth (kies), etc.
elguhr), diatomaceous earth, calcium carbonate, talc, powdered magnesia, fuller's earth, gypsum, spatula, diatomaceous earth
It can be in powder or granule form, including clay (h) and fillers such as china clay. This granule may be a preformed granule that is suitable for application to soil without subsequent treatment. These granules may be formed by impregnating filler pellets with the active ingredient or by pelletizing a mixture of active ingredient and powdered filler. Compositions for seed dressing include, for example, applying the set fI to seeds.
i. may contain agents that help the material to adhere (e.g. mineral oil); alternatively, the active ingredient may be formulated for seed dressing purposes using organic solvents (e.g. N-methylpyrrolidone or dimethylformamide); can.

Also to the composition of the invention. A dispersible powder containing a wetting agent that facilitates the dispersion of the powder or particles in a liquid.

It can be in the form of granules or particles. Such powders or particles may also contain fillers and suspending agents.

One or more active ingredients in an organic mulch agent optionally containing one or more wetting agents, dispersing agents or emulsifying agents.
An aqueous dispersion or emulsion can then be prepared by adding the mixture thus obtained to water which may also contain one or more wetting agents, dispersants or emulsifiers. can. Ethylene diflora 1 as a suitable dominant solvent,
Soprobyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, xylenes, trichloroethylene, fluorine alcohol, tetrahydrofurfuryl alcohol and glycol ethers (e.g. 2-ethoxyethanol and copoxyethanol) It is.

The 81-parabolite of the present invention to be used as a spray liquid includes a propellant,
For example, if the preparation is placed in a container under pressure in the presence of fluorotrichloromethane or dichlorodifluoromethane f'Ik
It can also be in the form of an aerosol.

The compounds of the present invention can be mixed dry with carpenter's mixture to form a composition suitable for sealing and generating smoke having the active ingredient Compound 1 in the fC space.

Alternatively, a compound of the invention can be used in microencapsulated form. , the compounds can also be formulated into biodegradable polymeric compositions to provide slow and controlled release of the active substance.

By including suitable additives, such as sixth additives that improve dispersion, adhesion and weather resistance of the treated surface, different compositions can be tailored to different applications.

The compounds of the invention can be used in mixtures with fertilizers (eg nitrogen-containing, potassium-containing or phosphorus-containing fertilizers). Preference is given to compositions incorporating the compounds of the invention, such as fertilizer granules miller 9 coated with said compounds. It is suitable to contain up to 23% of such finely divided active ingredient compounds.

The present invention also provides a fertilizer composition containing a compound of the general formula (lv) or a salt or metal complex of the above formula (lv).

The compositions of the invention may also be in the form of solutions for use as dipping or spraying liquids, which generally include one or more surfactants such as wetting agents, dispersing agents, emulsifying agents or suspending agents. are aqueous dispersions or emulsions containing the active ingredient in the presence of; and spray compositions of the type suitable for use in RIJ spray techniques.

The above agents may be cationic, anionic or non-ionic. Suitable cationic agents include quaternary ammonium compounds such as cetyltrimethylammonium bromide.

Suitable anionic agents include soaps, salts of aliphatic monoesters of sulfuric acid (e.g. sodium lauryl sulfate) and salts of sulfonated aromatic compounds (e.g. sodium dodecylbenzenesulfonate, sodium lignosulfonate, calcium or ammonium sulfate, butylnaphthalene sulfonate, and a mixture of the sodium salts of di-propyl and triisopropyl-naphthalene sulfonic acids).

Suitable non-one-ionic agents are the condensation products of fatty alcohols such as ocyl alcohol or cetyl alcohol with ethylene oxide or the condensation products of ethylene oxide with alkyl phenols such as octylphenol or nonylphenol and octylcresol. Other non-one-ionic agents are rt partial esters derived from long chain fatty acids and hexitol anhydride, condensation products of ethylene oxide and said partial esters, and lecithin.

Suitable suspending agents are parent wood colloids (eg λ-polyvinylpyrrolidone and sodium carboxymethyl cellulose) and vegetable gums (eg acacia and tragacanth).

Compositions for use as aqueous dispersions or emulsions are generally supplied in the form of concentrates containing a high proportion of one or more active ingredients. The concentrate is diluted with water before use. These concentrated liquids often withstand storage for long periods of time;
After such storage, an aqueous solution can be diluted with water to form an aqueous solution that remains homogeneous long enough to enable application by conventional electric spray equipment. What about concentrated liquid? -rVLt may conveniently contain one or more active ingredients at 1, suitably 1 o-rs+Ic
X, for example λj ~ 60, of the active ingredient. It is suitable to contain an organic acid (for example, an alkaryl or aryl sulfonic acid such as dodecylbenzenesulfonic acid in xylene sulfone Ct) in the concentrated acetate. This is because the presence of such organic acids can increase the solubility of one or more active ingredients in the polar solvents often used in the concentrate. Since the concentrate contains a commercial proportion of surfactant per fcm, a sufficiently stable emulsion in water is obtained.

After dilution to form an aqueous solvent, such solutions may contain an amount of one or more active ingredients depending on the intended purpose, but not exceeding 0,000 Nht or 0.0
/ one or more of 9C% to 10% by weight.

An aqueous solution containing the above active ingredients can be used.

Also to the composition of the invention. One or more other biologically active 1ζ compounds also include compounds with similar or complementary fungicidal activity, or compounds with plant growth regulating activity, herbicidal activity or insecticidal activity. It can contain.

The other fungal compounds are 1, for example, 5eptoria*G.
ibberella and Helmlnlhospori
Diseases of ears of grains (e.g. wheat) such as um spp.
It can be said that it is a compound capable of eradicating vola and soil-borne diseases, downy mildew and powdery mildew of grapes, and powdery mildew and scab of apples. These fungicide mixtures can have a wide range of activity even when the compound of the general formula (/l) alone has a wide range of activity. Examples of said other fungicidal compounds are carbe/guzim, benomyl, thiophenate-methyl, thiabenguzole, fuveridazole, erridazole, dichlofluanid, tamoxanil.

Oxacyxyl, Offrace, Metalaxyl, Furaxyl, Benalaxyl, Fosetyl Aluminum, Fenarimol s1 Zolodione, Procymidione, Vinclozolin, Penconazole, Myclobutanil, FLO/! /29
7.83301, Virazophos, x f IJ %
-ru, citarimphos, tridemorph, triphorine.

Nuarimol, triazbutyl, guazatine, gloviconazole, prochloraz, flutriafol, chlortriafol i.e. drugs /-(/, co, ≠-triazole
-l-yl)-2-(,2,4A-dichlorophenyl)hexane-cool, DPXH6ry3(/ -(
(Bisuzhenyl-fluorophenyl)methyl7lyl]methyl) / H-/ * J 9 μm triazole, triaziphone, triadimenol, diclobuturazole,
Fenopropimorph, Fenprovisi/, Triazomorph, Imazalil, Fenflam, Carboxin, Oxycarboxin, Mesfuroxam, Dobumorph, BA
8 4cj44. Plasticidin S, Kasugamazushin,
Ejihue/Hos.

Kitazine P1 phthalibeta, globenazole, 1tubrothiolane, tridiclazole, biloquilan, chlorobenzthiacin, neoandin, polyoxin D, IZ+j! Mycinin, regronil, flutolanil, pencucron,
Diclomedine, 7enazine oxide, nickel dimethyl dithiocarbamate, tecroftalam, bitertanol, pubilimate.

, etaconazole, stregtomycin, ciboflam,
Pyroxazole, chinomethionate, dimethisomol,
fenapanil, dorclofos-methyl.

Biloxiflu, Polylam, Maneb, Mancozeb, Kabutafor, Chlorothalonil, Anisidine, Thiram, Cagtan, Folpet, Zineb, Propineb, Sulfur, Dinocap, Vinanozecryl, Nitrotal Imp-A Pill, Dodine, Dithianone.

Fentin, hydroxide, fentin acetate, tecnazeno, quintoze/, dichlorane, copper-containing compounds such as oxidoxychloride, copper sulfate and bold, and organic mercury compounds such as / -(2-cyanocomethoxyiminoacetyl) -3-ditylurea etaconazole and fenpropemorph.

Compounds of general formula (11) may be mixed with soil, peat or other root media to protect plants from atom-borne diseases, ±4-borne diseases or foliar fungal diseases.

Suitable insecticides such as pirimicarp, dimethoate.

Damaton-3-methyl, formothion, carnosuril,
1-amprocarp, XMOlBPMO, carbofuran, carbosul-7an, diazinon, fenthion, fenitrothion, fue/toate, chlorpyrifos, inxathion, propafos, monocrotopus, zoprofezine, esloproxyfen and cyclobrothrin.

The above-mentioned plant growth regulating compound has a seed head shape 11
For example, 4.
It may selectively regulate the growth of the species.

Examples of plant growth regulating compounds suitable for use with the aromatic products of the invention include gipperellin (e.g. dA3, dA4 or dA, >
.

Auxins (e.g. indoleacetic acid, indolebutyric acid,
naphthoxyacetic acid or naphthyl acetic acid), cytokinin (e.g. kinetin, diphenylurea, benzimidazole, benzyladenine or benzylaminopurine), phenoxyacetic acid (e.g. λ-Hori or MCPA), substituted benzoic acid (e.g. triiodobenzoic acid) 1 mol. actin (e.g. chlorfluorechol), maleic hydrazide,
Glyphosate, glyphosine, long chain fatty alcohols and fatty acids, dikegratuc, bacbuturazole, flurpyrimidol, fluoridamide, mefluidide.

Substituted quaternary ammonium and phosphonium compounds (eg chlormequat, chlorphonium or mepiquat chloride), ethephon, carpetamide.

Methyl-J, A-dichloroanisate, daminozide, aslam, abscisic acid, isopyrimole.

/-(4!-chlorophenyl)-”16-cymethyl-2
-Oxo-1, Kojig P ropyridine-3-carzenic acid, hydroxybenzonitrile (e.g. bromoxynil)
, difuenzocort, pensoylzolozoethyl 3.6-
These are dichloropicolinic acid, fenpentezole, inabenfide, triabentenol and technazene.

The invention is illustrated by the following examples, where temperatures are given in °C.

Example 1 This example shows that Hiro-[λ-(p-t-butylphenyl)-cyclozolobylmethyltwo-piperidine (Compound A in Table 1/
) production is explained.

Ethyl diazoacetate (ri, 711f, 0.0rjt mol > 1-, in dichloromethane (200111),
Injected over a period of time at 0°C into a solution of pt-butylstyrene (/Lj/f, 0.01 #mol) and anhydrous sulfuric acid steel (O0/l) in dichloromethane (jOvt). Add dropwise by Denzo. Dichloromethane is distilled off during the addition. After complete addition, residual dichloromethane is removed in vacuo and the resulting brown oil is purified by column chromatography (silica eluted with petroleum ether: ethyl acetate μ:l) to give ethyl co-(p
-t-butylphenyl)-cyclozolonocenecalzexylene) (10%) is obtained.

Ethylco (p, -t-)f ruphenyl)-cyclopronogne calxylate (/0.coJf, 0.044
λ mol) wo, lithium aluminum hydride suspended in diethyl ether dried with sodium (/, ri y, 0
．． 0° C. mol) dropwise at room temperature. After complete addition, the solution is stirred for a further 2 hours at room temperature.

Ethyl acetate (-27+d) was added carefully dropwise, the mixture was poured into water and extracted with diethyl ether (100 yd). Wash the ethereal extract with water and add anhydrous sulfuric acid)
After drying on an IJ column and evaporating the solvent, J-(p-t-butylphenyl)-cycloprobylmethanol (OS) is obtained as a colorless liquid. Methanesulfonyl chloride (z, yat, o, oza mol) Co(p-t-butylphenyl)-cyclopropylmethanol (Hiro, 72y,
o, oλ3 mol) and stirred at room temperature for 10 hours. The mixture was poured into water and diethyl ether (-
The ethereal extract was extracted with water (4(x
7j, g) and dried over anhydrous sodium sulfate. When the solvent is removed, J-(p-t-i
tylphenyl)-cyclopropylmethyl chloride is obtained, which is used in the final step without purification.

Dissolved in pyridine (10wt) 9-(pt-butylphenyl)-cyclopropylmethylchloride?" to
, s3t, +17. oo co≠mol) and piperidine (/l
ut.

0.01 mol) and heated to 0° C. for 10 hours.

After cooling to room temperature, the mixture is poured into water and extracted with diethyl ether. Wash the ethereal extract with water.

Drying over anhydrous sodium sulfate and removal of the solvent yielded an orange oil. Purification of this oil using six column chromatography (silica gel eluted with petroleum ether: ethyl acetate = /:/) yielded the title compound as a pale yellow-white oil. (0, J
f, cis:trans CH Tomi/At=/:ri)
get.

Example This example is about Hiroshi-[yo(pt-butylphenyl)-
3,,! -dimethylcyclopropylmethyl]-morpholine (compound mr of Table I) is described. isozolopylphenylphosphonium iosito (co, 4Ly,
After complete addition, the solution was stirred at -j°C for 30 min and poured into dry tetrahydrofuran (10 wrl) at -t'. t-butyl-ethylcinname) (10f.

Add dropwise at 0.04 U 3 mol>ts°C. Let the solution warm up to room temperature, at room temperature! Stir for a while and then soak in water.

Extract with diethyl ether. The ethereal extract is washed with water, dried over anhydrous sodium sulphate and evaporated to give an orange oil. This oil is dissolved in chloroform (jOwit) and stirred with cuprous chloride (jf) to evaporate the chloroform. The residue was dissolved in ether (jQm) and F
When the ether is removed, ethyl 2-
(p-1-butylphenyl)-J,J-,)methylcyclozolonocalcexylene) (/J, λt) is obtained, which is used in the next step without further purification. Ethylyo(pt-1 tylphenyl)-J,! --)) 5-Luciclopronocardioxyle) <! ,71,0.
032 mol) gold, lithium aluminum hydride suspended in diethyl ether (JOd) i/, 2f, 0.03
1 mol) dropwise at room temperature. After stirring for an hour at room temperature, ethyl acetate was added, the mixture was poured into water (jOt), and diethyl ether (2% J0-) was added.
) to extract. The ethereal extract was dissolved in water (4CXj(7-
) and dried over anhydrous sodium sulfate.

Removal of the solvent yields -2-(p-t-butylphenyl)-3,3-')methylcyclopronozonemethanol (7,tf)t- as a yellow oil.

Methanesulfonyl chloride (J, j+d) was dissolved in pyridine (3jd) to give λ-(p-1-butylphenyl)-J, J-dimethylcyclopronogne methanol (λ, coy, o, o≠mol). ) dropwise at 70°C. After the addition the mixture was stirred at room temperature for 10 hours,
Extract with 10N HCl (107) and diethyl ether. The combined ethereal extracts are washed with water (Hiroshi x 7JM), dried over anhydrous sodium sulfate and the solvent removed to give a colorless oil. High performance liquid chromatography (hptc) (
When purified by silica (eluted with hexane), io(
pt-butylphenyl)-J, j-dimethylcyclopropanemethylchloride r<s,zy>2 is obtained.

io(p-1-butylphenyl)-J,j-dimethylcyclozolonomethylchlorider (o,tr tOo
o 03 mol) and morpholine (0.01 mol, o, oo
B mol) and triethylamine <0.69.0.006 mol) are stirred at 2ro° C. for 10 hours. The solution was cooled to room temperature and poured into water (20wt). The ethereal extract is washed with water to remove the solvent, yielding the title compound as a colorless oil.

Example 3 This example Fip-cλ-(pt-butylphenyl)-
) lance-cyclopropylmethyl)-,2゜6-cis-
The production of dimethylmorpholine (compound Bianhong in Table 1) will be explained. Ethylco(p-1-butylphenyl)-cyclopronozonecalxylene) (r, Of, 0.OJJ
! Mok)? Potassium hydroxide (J
,4j9,0,06! mol) is added dropwise at room temperature.

The solution was refluxed for 3 hours, cooled to room temperature and JMHCt
Neutralize carefully. Saturated sodium chloride was added and the aqueous solution was extracted with ethyl acetate (u x 100 #1g).

Dry over anhydrous sodium sulfate. Removal of the solvent yields λ-(pt-tithylphenyl)-cyclopropanecarginic acid (7,tf) as a white crystalline solid (mep, j!r~60<0>C).

Co(p-1-butylphenyl)-cyclopronozonecarzenic acid (7,fy,0
．． 036 mol) and oxalyl chloride (!, j f .

0.0443 mol) was stirred at room temperature for 3 hours.

Then, it is heated at 60°C for 2 hours. Removal of hexane and excess oxalyl chloride in full vacuum affords co(p-t-i tylphenyl)-cyclopropane carzenyl chloride as a pale yellow liquid, which is used in the next step for further purification.

2.6-dimethylmorpholine (ri, J f , θ, oo
r mol) gold, sodium dry ether (≠omt>
Dissolve tl-(pt-butylphenyl)-cyclopronozone carzenyl chlorite (Hiro, 96f).

A solution of 0.0 λ mol) is added dropwise at 0.degree. C. and after complete addition the solution is stirred at 0.degree. C. for 3 hours. Put the reactant in water＼
and extracted with diethyl ether (2 x 1007). The ethereal extract was washed with water and dried over anhydrous sodium sulfate, and removal of the solvent gave an orange oil (J-(pt
-butylphenyl)-cyclozolono7ane]carzenylco, 6-dimethylmorpholine (6t) is obtained.

Dissolved in diethyl ether (10-) dried with sodium :A, )+7
) solution in diethyl ether dried over sodium
Lithium aluminum hydride (20ml) suspended in
0.2f.

0.0013 mol), and the mixture f20
Stir at ℃ for 3 hours. The reaction mixture was poured into water and extracted with diethyl ether. Wash the ethereal extract with water (7,
Drying over anhydrous sodium sulfate removes the solvent to obtain a colorless oil. This oil was purified by column chromatography (silica gel eluted with ethyl acetate, 1:1 petroleum ether) to give a /J□ nmr (from TMS to p
shift in pm) c-1/4c7. Tatar C-g
S ri, 2 ko 1 O-J / 3 ri, 3'yy
c-2344, 0710-J /λj, /'11
0-10 J, /, here 2 (3-II/koμ, riλ
7a-ii λl', 1g (3-j 7/,
3uj O-fuco 20,01! c-662, ri14
2(1-/j/de, 06!0-7 jri, j3λ
O-/4! /4',4iGj Example μ This example describes the preparation of Hiro-[co(p-trimethylsilylphenyl)-trans-cyclopropylmethyl-4,4-cis-dimethylmorpholine (compound 5n133 of Table 1). n-Butyllithium (0, fucomole, 7
．． Dissolve 77.6 me of a 6M solution in dry tetrahydrofuran (/tcp) under nitrogen.
- Add dropwise to a solution of bromostyrene (Co/Af, 0./2 mol) at -60°C to -70°C. After complete addition, the reaction mixture was stirred for 7.3 hours at -tO<0>C and treated with trimethylsilyl chloride (/2rf, 072 mol) tl--10
℃ and an additional 0.1 hour after addition! Stir at θ°C. The mixture is stirred at room temperature for 1 hour, poured carefully into water and extracted with diethyl ether. The ethereal extract was washed with water (x3), dried over anhydrous sodium sulfate,
Removal of the solvent yields an orange oil. Purification by column chromatography [silica gel eluted with petroleum ether (bp-a o ~ 60°C)] gives p-
Trimethylsilylstyrene (7!, RiO2, Ri/, 2%
).

Ethyl diazoacetate (/7.tF, 0.11 mol) in dry dichloromethane (2jOe) and p-trimethylsilylstyrene (/1131, 0.103 mol) dissolved in dry dichloromethane (to, 5) and sulfuric anhydride. 3. In a solution with steel (0hiroP) at 0°C. Add drops via infusion pump over the course of the evening hours. Dichloromethane is distilled across the trap during the addition. After complete addition, the residual dichloromethane was removed in vacuo and the resulting brown oil was purified by column chromatography (silica gel eluted with petroleum ether: ethyl acetate nibs:l) to give ethylcot (p-
4-dimethylsilylphenyl)-cyclopropanecarboxylate (/3ft, J-1%) was obtained.

Ethyl λ-(p-trimethylsilylphenyl)-cyclopropanecarboxylate) (/j, 7F.

Potassium hydroxide (344f,
A solution of 0.10 j mol) is added dropwise at room temperature. The solution!
Reflux for an hour, cool to room temperature and carefully neutralize with xMHcz'. Saturated sodium chloride is added and the aqueous solution is extracted with ethyl acetate (<<xltO-) and dried over anhydrous sodium sulfate. Removal of the solvent yields x-(p-trimethylsilylphenyl)-cyclopropanecarboxylic acid (/1.6t, 3%) as a white crystalline solid.

2-(p-trimethylsilylphenyl)-cyclopropanecarbo/acid (t
i, tv, o, oz mol) and oxalyl chloride (ltry y
, o, iz mol) was allowed to stir at room temperature for 1 hour;
Then, it is heated at 60°C for 3 hours. When hexane and excess oxalyl chloride are removed in vacuo, a pale yellow liquid -
2-(p-)limethylsilylfer)-cyclopropanecarbonyl chloride (l, 1 t, 7 jX)
is obtained and used in the next step without further purification.

2.6-Dimethylmorpholine (22λf, 0.12 mol) was dissolved in sodium-dried ether (100%)-2-(p-trimethylsilyl7enyl)-cyclopropanecarbonyl chloride (/222%). It is added dropwise at io<0>C to a solution of OO (mol) and, after complete addition, the solution is stirred at 20[deg.]C for 3 hours. The reaction mixture was poured into water and extracted with diethyl ether (coX/jO-). The ethereal extract is washed with water, dried over anhydrous sodium sulfate, and the solvent is removed to yield 2-(p-trimethylsilylphenyl)-cyclopropanecarbonyl-2,t-dimethylmorpholine (/a,/f).

A solution of 2-(p-trimethylsilylphenyl)-cyclopropanecarbonyl-x,ty-cy)thylmorpholine (32 μt, o, oiλ mol) in diethyl ether (2!-) dried over sodium was added to Lithium aluminum hydride (o, txt, o,
mol) is added dropwise to the suspension and the mixture is stirred at 20° C. for 3 hours. The reaction mixture was poured into water and extracted with diethyl ether. The ethereal extract is washed with water, dried over anhydrous sodium sulfate, and the solvent removed to give a colorless oil. Purification of this oil by column chromatography (silica gel eluted with ethyl acetate/petroleum ether A/:i) gives the title compound (XOt). Two other isomers (compounds &/32 and /JIA of Table 1) were also isolated.

Example ! This example shows u-(2-(p-17butylphenyl)
-comethyl-trans-cyclopropylmethyl)-J
, 4-cis-dimethylmorpholine (91 compounds Na/
Explain the manufacturing process. Sodium hydride (rust, ozoxm suspension in oil, 0./1 mol) was washed with petroleum ether and KWA suspended in dry DMSO (riO-), 6
Heat with stirring to 0-70°C for 2.3 hours. The reaction mixture was then cooled to lj°C and methyltriphenylphosphonium bromide (μo, tt, o, timole) was added to
0. Add in portions with rapid stirring over a period of time. After the addition, the reaction mixture was stirred for an additional hour at room temperature and added with F-1-butylacetophenone (0.01°C).
/ 1 mol) is added dropwise over a period of 7 hours.

The resulting reaction mixture was stirred at room temperature for /J hours and diluted with water (, z
s o mt )-IiC so\gi, ether (g
/rowt). Add the ethereal extract to water (
v,×io.

-) and dried over anhydrous sodium sulfate.

Removal of the solvent gave an orange oil, which was purified by column Chromadog 2F (silica gel eluted with petroleum ether) to give a colorless liquid α-methyl-Hiro=t-butylstyrene (/7.rJ?).

0%).

Ethyl diazoacetate (13, rif, 0.12 mol) in dry dichloromethane <xoowt) was dissolved in α-methyl-
A solution of et-butylstyrene (/'1411, 0.10 mol) and anhydrous cuprous sulfate (0, J t ) was heated at 0°C.
and are added dropwise via an infusion pump over a period of 3 hours. Dichloromethane is distilled off over the course of the addition. After the addition is complete, the residual dichloromethane is removed in vacuo and the resulting brown oil is purified by column chromatography (silica gel eluted with petroleum ether: ethyl acetate=liquid:l) to give a colorless oil, tositeethyl! -(pt-butylphenyl)-nomethylcyclopropanecarboxylate (
/! Jf, 7J, 4%).

Ethyl 2-(pt-7'tylphenyl)-2-methylcyclopropanecarboxylate (/J', F?.

Potassium hydroxide (r, 0.07 J mol) dissolved in methanol (/4 jm) and water (747 m)
/ Jt, o, iaz mol) is added dropwise at room temperature. The solution was refluxed for μ h, cooled to room temperature, and purified with MHC.
Carefully neutralize with t. Saturated sodium chloride was added and the aqueous solution was extracted with ethyl acetate (4!X/OII+/),
Dry over anhydrous sodium sulfate. When the solvent is removed, λ-(p-t-butylphenyl)-
No-methylcyclopropanecarboxylic acid (16, rit, i
oo%).

No(pt-butylphenyl)-2-methylcyclopropanecarboxylic acid (lt
, 2f, 0.07 mol) and oxalyl chloride (/LJf,
0.1 mol) was stirred at room temperature for 1 hour and then t
Warm at 0°C for 3 hours. Hexane and excess oxalyl chloride were removed in vacuo to give a pale yellow liquid J-(p-t
-butylphenyl)-2-methylcyclopropanecarboxyl chloride (/7#f, 100%), which is used in the next step without further purification.

6-Dimethylmorpholine (/s, 6t, o, Hiromol) was dissolved in sodium-dried ether (At-). 2- (p-t-butylphenyl)-λ-
Methylcyclopropane carbonyl chloride (Ir, 6
f, 0.03 j mol) dropwise at 10°C, and after the addition is complete the solution is stirred at 20°C for J, 7 hours. The reaction mixture was poured into water and diluted with diethyl ether (xxltQ).
Extract with y). The ethereal extract was washed with water, dried over anhydrous sulfuric acid, and the solvent removed to give J-(
1) -t-butylphenyl)-2-methylcyclopropanecarbonyl-2,a-dimethylmorpholine (/Yti
-y, ioo%)! obtain.

of Nor(pt-butylphenyl)-2-methylcyclopropanecarbonyl-s,g-dimethylmorpholine (//, IP, 0.03.6 mol) in sodium-dried ether (40 ttdl). The solution was dissolved in lithium aluminum hydride (1,6f, 0.0'12
mol) dropwise to the suspension and the mixture is stirred at room temperature for 3 hours. The reaction mixture was carefully poured into water and extracted with diethyl ether. The ethereal extract is washed with water, dried over anhydrous sodium sulfate, and the solvent removed to give a colorless oil. This oil was subjected to two-layer chromatography (ethyl acetate/
Purification by silica gel eluting with petroleum ether/:l gives the title compound (/, j f ). Two other isomers (compounds 1&L/4 and/7 of Table I) were also isolated.

Example 6 This example is μ-(-2-(pt-propylphenyl)-3-methyl-trans-cyclopropylmethyl]-
Co, t-cis dimethylmorpholine (compound 91
) production is explained. Sodium hydride (2 t, 10% suspension in oil, o, iz mol) was washed with petroleum ether and suspended in dry DMSO (lxO-), to ~70
Heat at 0 for an hour while stirring. The reaction mixture was then cooled to 75°C and ethyltriphenylphosphonium bromide (!741f, 0./!-F-k) was added to Q, 5
Add in portions with rapid stirring over a period of time. After the addition, the reaction mixture was stirred for an additional hour at room temperature and
i-Propylbenzaldehyde (201,0,13 mol) is added dropwise over a period of 1 hour. The resulting reaction mixture was stirred at room temperature for 12 hours and then poured into water (so omt).
and extract with ether (4xltQ*).

The ethereal extract was washed with water (≠X/00d),
Dry over anhydrous sodium sulfate. Removal of the solvent gave a yellow oil which was purified by column chromatography (silica gel eluted with petroleum ether: ethyl acetate = 1:1) to give p-methyl-i-propylstyrene (t
y, ot, you).

Ethyl diazoacetate (/3.otp, o, 71 mol) in dry dichloromethane (1jOyd) β-methyl-1-propylstyrene (110?, 0.71 mol) dissolved in dry dichloromethane (!Ovrl)
and anhydrous copper sulfate (0, J t ) at 20° C. over a period of 3 hours via an injection pump.

Dichloromethane is distilled off during the addition. After the addition is complete, residual dichloromethane is removed in vacuo and the resulting brown oil is purified by column chromatography (silica gel eluted with petroleum ether:ethyl acetate) to give ethylco(p-i-propylphenyl)-3- Methyl cyclopropane carboxylate (Cot, Of, Ri4
%).

Ethyl J-(+)-i-propylphenyl)-3-methylcyclopropanecarboxylate (244ft, 0
．． Potassium hydroxide (/31 mol) dissolved in methanol (/3owl) and water (/J0w1)
, 0.23 mol) is added dropwise at room temperature.

The solution is refluxed for 3 hours, cooled to room temperature and carefully neutralized with JMHCl. Saturated sodium chloride is added and the aqueous solution is extracted with ethyl acetate (px/lO*) and dried over anhydrous sodium sulfate.

Removal of the solvent yields -2-(p-,-t-propylphenyl)-3-methylcyclopropanecarboxylic acid<i'io
t.

7t%).

He-+fy (te'omt) K added J-(p-
A mixture of i-propylphenyl)-3-methylcyclopropanecarboxylic acid (l 7f, 0.07 mol) and oxalyl chloride (IO?, 0.0 t mol) was allowed to stir at room temperature for 2 hours and then at 60 °C. Warm for 3 hours. Removal of hexane and excess oxalyl chloride in vacuo yields J-(p-i-propylphenyl)-J-methylcyclopropanecarbonyl chloride (izot, to
ot), which is used in the next step without further purification.

Ether (IAOm) obtained by drying λ,6-dimethylmorpholine (j,Of, 0.0 h 3 mol) with sodium
Co(p-i-propylphenyl)-3-methylcyclopropanecarbonylchloride (j:or,
Add dropwise at 10° C. to a solution of 1 mole of O, O) at 10° C. and stir the solution at 20° C. for 3 hours after the addition is complete. The reaction mixture was poured into water and extracted with diethyl ether (2 x 100ml). The ethereal extract was washed with water, dried over anhydrous sodium sulfate, and the solvent removed to give Co(p-i-furobylphenol)-3-methylcyclopropanecarbonyl-,2,4-dimethylmorpholine (b) as a yellow oil.
, 3t, ri! %).

Dissolved in ether (3o-) dried with sodium,
*J-(p-t-propylphenyl-3-methylcyclopropanecarbonyl-2,6-dimethylmorpholine (!, rf, 0.0/r mol) solution in sodium-dried ether (J o, t ) K suspended lithium aluminum hydride (o, ty.

0.02 mol) and the mixture was stirred at room temperature for 3.0 mol.
Stir for an hour. The reaction mixture was carefully poured into water and extracted with diethyl ether. The ethereal extract is washed with water, dried over anhydrous sodium sulfate, and the solvent removed to give a colorless oil. Purification of this oil by column chromatography (silica gel eluted with ethyl acetate/petroleum ether 2:3) gives the title compound (/, 11). Three other isomers (compounds of Table 1) were also isolated.

Example 7 A L9 milk # is formed by mixing the following ingredients and stirring the mixture sonically until all bI is dissolved.

Compound of Example I to% ethylene dichloride μO% P-decylbenzenesulfonate calcium 5% [Luprole JL
10% [Aromasol JH3! % Example r A composition in the form of particles readily dispersible in a liquid, e.g. Dry the mixture through a British standard mesh sieve, dimensions a a -
, -i 0 (7f passage to obtain the desired particle size.

Compound of Example 2! O% [Dispersol] T coj% "Lubrol JAPN, t
t3% sodium acetate 2
3. Example: All of the following ingredients are ground together to produce a powder composition #J that is easily dispersible in liquids.

Compound of Example 1 m7% [Jisunogsol JT 5% [Rezabol JNX
Oo, t% [Cero7as JBt00
co% sodium acetate g 7
j% Example i.

@ Surrounding component ke Liquid obtained by melting into solvent? Spray on the shank grains of china clay. Then, the solvent is completely evaporated to form a granular composition. Make a groan.

Compound of Example J j% china clay fine grains
9j% Example 11 Sealing r) A composition suitable for use as a lutzing agent is prepared by mixing the following three components.

Compound of Example 1 go% mineral oil
2% Pottery clay “′%
Example 7.2 Next effective ingredient? A powder is prepared by mixing with talc.

Compound of Example 2 3% Tal
the law of nature
Example 13 The following ingredients were milled and then dispersed by forming an aqueous suspension of the milled mixture and water.
1) Manufacture the composition.

Compound of Example 1 m0% "Dispersol JT 10% [Lubrol JAPNj
t% Water Example 1tL A dispersible powder composition is prepared by mixing all of the ingredients listed below together and then grinding the mixture until all are thoroughly mixed.

Compound of Example 2 2! % [Aerosol J
OT/B Co% [Dispersol JA, C
05% Pottery clay λ
t%, / 1J 0% Example 13 This example demonstrates the production of a dispersible powder composition.All the ingredients are mixed and the mixture is then ground in a pulverizer.

Compound of Example 1 Coj% [Nosebanal JBX/Ly.

"Jisuno Zoichi Sol JT t% polyvinylpyrroline 10% silica
XZZ pottery clay 3t
t% Example 16 The various ingredients listed below were mixed and then ground to form a dispersible powder.

Compound of Example λ 2j% [Aerosol J
OT/)l 2% “Dispersol JA
1% china clay 6t% In Examples 7-/A, the proportion of the given component is %.

Compounds listed in Table 1 and compounds A3 to 33 are Example 7
~l It is prescribed in the same manner as described in Part B.

A description of the composition or substance incorporated into the trademark name and song name is given below.
: A compound of nonylphenol (1 mole) (3 moles of hydroxyl); Romazole H: A solvent mixture of alkylbenzenes. Noshasol T&AC: A condensate of sodium and formaldehyde with sodium 7-talenesulfonate. Mixture Lubrol x PNj: Nonylphenol (1 mol)
Condensation product with Tona7talenoxy) I < z, z mol) Cello7as B6oo: Sodium calxoxymethyl cellulose II (Hyazole 1) Lysafol NX: Condensate with nonylphenol (1 mol) Tona7talene oxide (2 mol) 1 Aerosol OT/B: Dioctyl sodium sulfosuccinate no ξ-banal BX: Sodium Aljarna 7talenes sulfonate.

Example 17 The compound t% of the present Hakko was tested against diseases caused by the mold that parasiticizes leaves. The technique used is as follows.

The best, most common type, grown in John Innes pot compost (, lh/or 2) in a small pot with a diameter of 4' (Ill).
sol) Add T water to the solution and grind with a bead barrel, or dissolve the test compound in acetone or acetone/ethanol and dilute it all at once just before use. The test compound was formulated. For foliar diseases, a suspension containing 1/00 ppm of active ingredient is sprayed on the leaves and on the roots of the soil intermediates. The spray solution is applied to the leaves to maximum retention, and the roots are immersed so that the final concentration of active ingredient is approximately equivalent to 10 ppm of dry soil.

When applying the spray to whole grains, 20 TwePn were added to give a final strain of o, or %.

For trials in large cities, the test compound S is applied to the soil (roots) and leaves (by spraying) one or two days before the pest control.The exception is barley powdery mildew ( Erysi
phe graminis); in this case, 2 hours before treatment, the rodents were infected with the disease.
do. The foliar pathogen was applied as a spore suspension by spraying onto the leaves of the test rodents. The valuables were inoculated with the disease, placed in an inappropriate environment, allowed to become infected, and infected until the disease could be evaluated. The period from inoculation to disease evaluation was varied between 4 and 79 days depending on the persimmon species affected and the environment.

The disease control rate was recorded using the following grade: 2 μ = No disease occurred, J = Containing traces on untreated moose ~ j% disease, 6 ~ coj% green damage on untreated moose. l=26~ for unprocessed materials! 9% disease O = 40-100% disease on untreated plants The yields obtained are shown in Table III below.

Claims (1)

[Claims] 1. The following formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R^1, R^2, R^3, R^4, R^5 and R
^6 each represents a hydrogen atom, an alkyl group containing 1 to 4 carbon atoms, or a halogen atom, R^7 and R^8
each represent a hydrogen atom or an alkyl group containing 1 to 4 carbon atoms or together form a ring which may contain additional heteroatoms; X and Y each represent a hydrogen or halogen atom or alkyl, Cycloalkyl, alkenyl, alkynyl, aryl, aralkyl, alkoxy or aryloxy group or group: ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R^9, R^1^0 and R^1^1 are alkyl,
tertiary amine compounds, stereoisomers and acid addition salts thereof; 2. In the compound of formula (I), R^1, R^2,
R^3, R^4, R^5 and R^6 may be the same or different and represent a hydrogen atom, an alkyl group containing 1 to 4 carbon atoms, or a halogen atom; R^7 and R^ 8 may be the same or different and represent a hydrogen atom or an alkyl group containing 1 to 4 carbon atoms or may together contain oxygen, nitrogen or sulfur as additional heteroatoms and optionally forms a ring which may have a substituent; X and Y may be the same or different and are hydrogen or halogen atoms or alkyl groups containing 1 to 6 carbon atoms,
cycloalkyl groups containing 6 carbon atoms, each from 2 to
Alkenyl or alkynyl groups containing 6 carbon atoms, phenyl groups, benzyl groups, alkoxy groups, phenoxy groups, benzyloxy groups or groups containing 1 to 6 carbon atoms: ▲Mathematical formulas, chemical formulas, tables, etc. ▼ (wherein R^9, R^1^0 and R^1^1 may be the same or different and are alkyl groups containing up to 4 carbon atoms, each containing 2 to 4 carbon atoms 2. A compound according to claim 1, which represents an alkenyl or alkynyl group, a cycloalkyl group containing 3 to 6 carbon atoms or a phenyl group. 3. In the compound of formula (I), R^1 and R^
2 is hydrogen, halogen or C_1_-_4 alkyl group; R^3 and R^4 are hydrogen; R^5 and R^6
is hydrogen or a C_1_-_4 alkyl group; R^7 and R^8 are a C_1_-_4 alkyl group or together with adjacent N-atoms substituents a C_1_-_4 alkyl, phenyl or hydroxymethyl group form a piperidine, morpholine, thiomorpholine or piperazine ring which may have as; X and Y are hydrogen, halogen, C_1_~_
4 alkyl, C_1_~_4 alkoxy, phenyl, phenoxy, benzyl, benzyloxy or group: ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (In the formula, R^9, R^1^0 and R^1^1 are C_1_~
_4 alkyl group) according to claim 1 or 2. 4. In the compound of formula (I), R^1 and R^
2 is hydrogen, methyl or chlorine; R^3 and R^4 are hydrogen; R^5 and R^6 are hydrogen or methyl; R^7 and R^8 are piperidine, 3,5- dimethylpiperidine, morpholine, 2,6-dimethylmorpholine,
diethylamino, 4-phenylpiperidine, 3-hydroxymethylpiperidine, thiomorpholine, piperazine or 4-phenylpiperazine; X and Y are substituents at the 3- or 4-position of the phenyl ring, one of which is hydrogen or C_1_ _4 alkyl group, and the other is hydrogen, C
The compound according to any one of claims 1 to 3, which is a _1_-_4 alkyl, C_1_-_4 alkoxy, chlorine, bromine, phenyl, phenoxy, benzyl, benzyloxy, or a C_1_-_4 trialkylsilyl group. . 5. The following compounds ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (Compound N in Table I
O. 4) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Compound N in Table I
O. 15) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Compound N in Table I
O. 94) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Compound No. in Table 1
．． 133) Compound 6 according to claim 1, the following formula (II): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R^1, R^2, R^3, R^4, R^5, R^
6, X and Y are as shown below, and Z is a leaving group). R^8 is as below) in the presence of a convenient solvent or in the absence of a solvent at a temperature between 20 and 100°C. ▼(I) [In the formula, R^1, R^2, R^3, R^4, R^5 and R
^6 each represents a hydrogen atom, an alkyl group containing 1 to 4 carbon atoms, or a halogen atom, R^7 and R^8
each represent a hydrogen atom or an alkyl group containing 1 to 4 carbon atoms or together form a ring which may contain additional heteroatoms; X and Y each represent a hydrogen or halogen atom or alkyl, Cycloalkyl, alkenyl, alkynyl, aryl, aralkyl, alkoxy or aryloxy group or group: ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R^9, R^1^0 and R^1^1 are alkyl,
a tertiary amine compound representing an alkenyl, alkynyl, cycloalkyl or aryl group. 7. The compound of the above formula (II) has the following formula (IV): ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV) (In the formula, R^1, R^2, R^3, R^4, R^ 5, R^
6. prepared by treatment with tosyl chloride and, if desired, (a) of formula (IV) above (with the proviso that R^3 and R^
4 are both hydrogen), the alcohol has the following formula (V): ▲
There are mathematical formulas, chemical formulas, tables, etc.▼(V) (In the formula, R^1, R^2, R^5, R^6, X and Y are as above, and R^ is an alkyl group) prepared by treating the ester with a reducing agent in a convenient solvent, or (b) the above formula (IV), provided that R^3 and R^4
are both alkyl groups) is the alcohol of the above formula (V
) with excess alkylmagnesium halide or excess alkyllithium in a convenient solvent, said esters of formula (V) having the following formula (
VI): ▲Mathematical formulas, chemical formulas, tables, etc.▼(VI) (wherein R, R^5, R^6, X and Y are as above) in a convenient solvent. The following formula (VII
): ▲Mathematical formulas, chemical formulas, tables, etc.▼(VII) (wherein R^1 and R^2 are as above) prepared by reaction with phosphorane, or alternatively the above formula (V) (wherein R^5 is hydrogen) in a convenient solvent using a suitable catalyst, the ester of formula (VIII): ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼(VIII) (In the formula, R^1, R^2, R^6, X and Y are as above) prepared by adding ether diazoacetate to the olefin. The method according to claim 6. 8. The following formula (IX): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IX) (In the formula, R^1, R^2, R^5, R^6, R^7, R^
8, where X and Y are as below) is treated with a reducing agent in a convenient solvent. R^1, R^2, R^5 and R^6 each represent a hydrogen atom, an alkyl group containing 1 to 4 carbon atoms, or a halogen atom, and R^3 and R^4 each represent hydrogen; , R^7 and R^8 each represent a hydrogen atom or an alkyl group containing 1 to 4 carbon atoms or together form a ring which may contain additional heteroatoms; each hydrogen or halogen atom or alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl,
Alkoxy or aryloxy group or group: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^9, R^1^0 and R^1^1 are alkyl,
a tertiary amine compound representing an alkenyl, alkynyl, cycloalkyl or aryl group. 9. The following formula (X): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(X) (In the formula, R^1, R^2, R^5, R^6, X and Y are as above) preparing an amide of formula (IX) by reacting an acid chloride of formula (IX) in a convenient solvent with an amide of formula (III): ) is the acid chloride of the following formula (X I ): ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (X I ) (In the formula, R^1, R^2, R^5, R^6, X and Y are as above) is prepared by reacting an acid of the formula (X I ) with a conventional chlorinating agent in a convenient solvent;
As such, the acid of formula (V
9. A method according to claim 8, wherein the method is prepared by hydrolyzing an ester of ). 10. The following formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R^1, R^2, R^3, R^4, R^5 and R
^6 each represents a hydrogen atom, an alkyl group containing 1 to 4 carbon atoms, or a halogen atom, R^7 and R^8
each represent a hydrogen atom or an alkyl group containing 1 to 4 carbon atoms or together form a ring which may contain additional heteroatoms; X and Y each represent a hydrogen or halogen atom or alkyl, Cycloalkyl, alkenyl, alkynyl, aryl, aralkyl, alkoxy, or aryloxy group or group: ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R^9, R^1^0 and R^1^1 are alkyl,
A fungicidal composition comprising a tertiary amine compound (representing an alkenyl, alkynyl, cycloalkyl or aryl group) or an acid addition salt or stereoisomer thereof, and optionally a carrier or diluent.