JPS59110673A - 2-(substituted pyridyl)ethylphenyl ether derivative and its preparation - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I (R is lower alkyl; n is 1 or 2; X is halogen, lower haloalkyl; Z is nitro or amino) or its salt. EXAMPLE:2-Chloro-1-[2-(5-ethyl-2-pyridyl)ethoxy]-4-nitrobenzene. USE:Showing improved fungicidal effect on pathogenic fungi of plants of blast of rice plant, brown spot, scab, etc. of citrus fruits, etc., useful as an intermediate raw material for various kinds of compounds having physiological activity such as herbicidal action, etc. or a fungicidal composition for agriculture. PROCESS:For example, a compound shown by the formula II (is reacted with a compound shown by the formula III (Y is halogen) in a solvent in the presence of a base under cooling with ice - at 200 deg.C for 30min-20hr to give a compound shown by the formula I where Z is nitro. This compound is reduced to give a compound shown by the formula I where Z is amino.

Description

[Detailed Description of the Invention] Does the present invention have an excellent bactericidal effect against various plant disease pathogens?
[In the formula, R represents a lower alkyl group, n represents 1 or 2, and X represents a halogen atom or a lower haloalkyl group] This invention relates to a novel compound represented by or a salt thereof.

Until now, as a 2-<W-substituted pyridyl)alkyl phenyl ether derivative, unlike the compound (1) of the present invention, for example, 2-(6-methyl-2-pyridyl)ether-4 which has only a nitro group in the phenyl ring has been used. - Nitrophenyl ether. (Chemical and Pharmaceutical Bulletin (CBEM).

pHarm, Bull I), Vol. 80, p. 3580 (1982)] and 3-, which has no substituent on the pyridyl ring.
(3-Pyridyl)propyl 2-chloro-4-nitrophenyl ether (JP-A-56-189460) and the like have been reported, but nothing is known about the physiological activities of these compounds.

The present inventors continued their intensive research on 2-(substituted pyridyl)alkyl phenyl ether derivatives, and succeeded in producing the compound represented by formula (1) in excellent yield. 1) is an intermediate raw material for various compounds that exhibit superior bactericidal effects against plant disease pathogens such as rice blast, black spot of citrus, and scab compared to the above-mentioned known compounds, and also have physiological activities such as herbicidal activity. We have found that it is extremely useful as a. The present inventors further conducted various studies based on these findings, and as a result, completed the present invention.

That is, the present invention provides (11) a compound represented by formula (1) 71. or a salt thereof,
[The symbols in the formula have the same meanings as above] [In the formula,
Is Y a halogen atom? , X has the same meaning as defined above] and the presence of a base.

In the above formula D, examples of the lower alkyl group represented by R include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and 5ec-butyl.

Straight chain or branched carbon number 1 to 4 such as te-10-butyl
lower alkyl groups are used.

The halogen represented by X is, for example, fluorine.

Chlorine, bromine, iodine, etc. are used.

The lower haloalkyl group represented by X includes, for example, fluorine and chlorine in addition to the above-mentioned lower alkyl group.

Substituents substituted with 1 to 8 halogens such as bromine and iodine are used, and specific examples include fluoromethyl, difluoromethyl, trifluoromethyl, dichloromethyl, dibromomethyl, trichloromethyl, 2-fluoroethyl, 1,2-difluoromethyl, 212, 2-trichloroethyl, 8-fluoropropyl, 2,3-difluoropropyl, 8,8.8-)lifluoropropyl,
2. -Chloro-1-methylethyl, 2-chloropropyl.

Examples include 3-chloro-1-methylpropyl, 2-1-chloro-1-methylethyl, and the like.

Among the lower haloalkyl groups in item 11, preferably, for example,
difluoromethyl, dichloromethyl, dibromomethyl,
It is substituted with 2 to 3 halogens such as trifluoromethyl, or a methyl group. Examples of the salts of the compound [1) of the present invention include compound [1,] and inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, such as p-toluenesulfonic acid, -y acid, acetic acid, propionic acid, oxalic acid, and tartaric acid. Acid addition salts with organic acids such as , malic acid, succinic acid, maleic acid, and fumaric acid are used.

The compound (1) of the present invention or a salt thereof can be used to control rice blast fungi [
Pirjcularia oryzae
yzae)], citrus black spot fungus [diabolse
;7 Tori (Diaporthe citri )
It exhibits excellent bactericidal activity against various plant disease pathogens such as citrus scab fungus (Elsinoe fawce~tti), such as rice blast, black spot on citrus fruits such as tangerine, daidai, yuzu, and lemon. Shows excellent control effect 2 against plant diseases such as scab.

The compound ['l] of the present invention or a salt thereof is added to rice, mandarin orange,
It is possible to prevent the occurrence of diseases on the above-mentioned plants by spraying it on citrus fruits such as daidai, yuzu, lemon, etc. in advance, and it is also possible to prevent the occurrence of diseases on the above-mentioned plants by spraying it during the disease outbreak period (Secondly, to control the diseases on the above-mentioned plants) I can do it.

When using the compound [1] or its salt as a disinfectant composition for agricultural use, for example, rice cup 'a'N is used against rice blast disease.
It can be used from the time when it is grown in a W box until it is harvested after planting, and it can be safely used for the above-mentioned citrus fruits at any time from the time of cultivation to the time of harvest.

When using the compound CI) of the present invention as an agricultural fungicidal composition, compound (1) or a salt thereof is dissolved or dispersed in a suitable liquid carrier (for example, a solvent), and a suitable solid Carriers (e.g. diluents, fillers)
Mix or absorb with this, and if necessary, add more! 2. Emulsifiers, suspending agents, spreading agents, penetrating agents, wetting agents, thickeners, stabilizers, etc. are added to this, and it is used as dosage forms such as emulsions, wettable powders, powders, and granules. These preparations are
It can be prepared by a known method.

The appropriate weight ratio of compound [1] in the sterilizing composition to the entire sterilizing composition is about 20 to 80 Higashikawa weight ratio for emulsions and wettable powders, and about 1 to 10 weight for powders and granules. However, the blending ratio can be changed as appropriate depending on the conditions at the time of use and the occurrence of diseases. In use, emulsions and wettable powders are preferably diluted with water or the like (for example, 100 to 10,000 times) and then dispersed.

Liquid carriers (solvents) used in disinfectant compositions include, for example, water, alcohols (e.g. methyl alcohol, ethyl alcohol, ethylene glycol, etc.), ketones (e.g. acetone, methyl ether ketone, etc.), ethers (e.g. dioxane, etc.). , Teshirahid Kuchifuran,
cellsolve, etc.), aliphatic hydrocarbons (e.g. gasoline, kerosene, kerosene, fuel oil, etc.), aromatic hydrocarbons (e.g. benzene, toluene, quinolene, solvent naphtha, methylnaphthalene, etc.) and other halogenated Hydrocarbons (e.g. chloroform, carbon tetrachloride, etc.), acid amides (e.g. dimeterformdemide, etc.), esters (e.g. ethyl acetate, butyl acetate ester).

Glycerin esters of fatty acids, etc.),
A solvent such as acetonitrile (for example, acetonitrile) is suitable, and one or a mixture of two or more of these solvents may be used.

Solid carriers (diluents, bulking agents) include vegetable powders (eg soybean flour, tobacco flour, wheat flour, wood flour, etc.), mineral powders (eg kaolin, bentonite).

Clays such as acid clay, talcs such as talc powder, waxite powder, silicas such as diatom powder, mica powder, etc.) Furthermore, alumina, sulfur powder, calcium phosphate, activated carbon, etc. are also used, and one or more of these are used. using a mixture of

Examples of ointment bases include polyethylene glycol, pectin, polyhydric alcohol esters of higher fatty acids such as glyceryl monostearate, cellulose derivatives such as methylcellulose, sodium alginate, ben-1-nitrite, higher alcohols such as glycerol, etc. Polyhydric alcohols such as petrolatum, white petrolatum, liquid paraffin, lard, various vegetable oils, lanolin,
One or two of dehydrated lanolin, hydrogenated oil, waxes, resins, etc.
More than one type of surfactant, or those with various surfactants and other additives added thereto, can be selected as appropriate.

In addition, as surfactants used as emulsifiers, spreading agents, penetrants, dispersants, etc., soaps, polyoxyalkylaryl esters (e.g., nonal
, manufactured by Takemoto Yushi Ni), alkyl sulfate Jm (e.g., Emar 10 @, Emar 40 [available]).

(manufactured by Kao Atlas), alkyl sulfonates (e.g.
Neogeno, Nezugen T ■, Dai-Kogyo Seiyaku, ■ Made by Nini: Neoperex ■, manufactured by Kao Atlas Nini), polyethylene glycol ethers (e.g., Nocopol 85)
■, Noniball 100■, Nokoporumi 60■, manufactured by Sanyo Chemical Co., Ltd.), polyhydric alcohol esters (eg, Tween 20■, Tween 80■).

(manufactured by Kao Atlas KK) etc. are used.

When compound (1) or a salt thereof is used as an agricultural fungicidal composition, the amount of compound (1) to be used is about 5 g to 201, more preferably about 20 g to 100 I per are.
It is.

The compound [1'] of the present invention or a salt thereof is produced by reacting compound (If) and compound (Ill) in the presence of a base. Suitable bases include, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal hydrides such as sodium hydride;
An inorganic base such as soda lime, for example, a basic ion exchange resin [for example, DOWEX-1 (manufactured by Dow Chemical Company,
U.S.A.) Ambalist A-26 (0-Muandhes Co., Ltd.).

Quaternary ammonium salts such as [U.S.]], or organic bases such as tertiary amines such as tri-kingylamine and pyridine are used.

Compounds (n) and (1) as raw materials are usually used in a molar ratio close to 1:1, but in some cases they may be used in large excess.

This reaction is usually carried out in a solvent. Suitable solvents include benzene, toluene, xylene, hexane,
Hydrocarbons such as ligroin, ethers such as ethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether,
Chloroform.

Carbon tetrachloride, halogenated hydrocarbons such as dichloromethane, dimethylformamide, dimethylacetamide, N-
Amides such as methylpyrrolidone, dimethylsulfoxide, sulfolane, acetonitrile, etc. are used.

These solvents can be used alone, or, if necessary, two or more types can be used as a mixture in an appropriate ratio.

When carrying out reactions using these solvents, the bases used are hardly soluble in these organic solvents, so the reaction system is often a solid-liquid two-phase system. For example, benzyltriethylammonium chloride, dodecyl Quaternary ammonium compounds such as trimethylammonium chloride and hexadecyltrimethylammonium bromide; quaternary phosphants such as tetrabutylphosphonium chloride and triphenylmethylphosphonium iodide;
The reaction can be promoted by adding a phase transfer catalyst such as a fonium compound or synchrohexyl-18-crown-6.

Moreover, this reaction can also be carried out as CJ by a liquid-liquid two-phase reaction between an aqueous solution of a base and the above-mentioned solvent. In this case as well, the reaction is accelerated by adding the above-mentioned phase transfer catalyst.
Bamboo can be used advantageously.

The phase transfer catalyst may be used in an amount of about 0.01 to 0.5 mol, preferably about 0.05 to 0.11 mol, per 0.91 mol of the compound.

The reaction can usually be carried out under water cooling or at 200°C, but an appropriate reaction temperature is selected depending on the type of compound CI) used, the base, the solvent, etc.

The reaction time is usually about 30 minutes to 20 hours, but in many cases about 1 to 5 hours is sufficient.

Further, a compound represented by the formula [the symbols in the formula have the same meanings as above] or a salt thereof can be produced by subjecting the compound CI') "a:>" to the A primary reaction.

This reduction reaction can be carried out using catalytic reduction means 7. That is, the reaction is carried out by shaking or stirring the compound [10] in a suitable solvent in the presence of a catalyst for catalytic reduction in a hydrogen stream. Suitable catalysts for catalytic reduction include, for example, platinum black, platinum dioxide, palladium black, palladium carbon, and Raney nickel.

Examples of commonly used solvents include water, alcohols such as methanol and ethanol, dioxane, tetrahydrofuran, dimethylformamide, and mixed solvents thereof. The reaction is usually carried out at room temperature and normal pressure, but may also be carried out under pressure or with heating. The reaction is completed in about 1 to 8 hours.

Further, the compound [t''] is produced by subjecting the compound [■'] to a reduction reaction using a transition metal such as iron or lead and an acid.

Suitable acids include, for example, inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as formic acid. In this reaction, the acid is usually used in a fit of about 0.1 mol or more, and can also be used in large excess to serve as a solvent.

The amount of transition metals such as iron and zinc used in this reaction is about 1 to 3 moles per mole of compound (1').

This reaction is carried out at a temperature ranging from room temperature to about 100°C.

The reaction time varies depending on the reaction temperature, etc., but is about 1 to 2 hours.

In this way l! The compound [(] is a known means,
For example, silk, vacuum concentration, 9-fraction distillation, solvent extraction, pseudo conversion, dissolution transfer, and chromatography.

Purification by crystallization, recrystallization, etc., single if! It is possible to do 1t1-.

The compound [1] of the present invention or a salt thereof can be obtained by a method known per se (for example, JP-A-56-189460) using a formula having herbicidal activity [wherein R' is a lower alkyl group or a lower alkokene group] The symbol has the same meaning as above. ') can be led to the compound represented by 3. More specifically, the compound [■1
] is, for example, a biridylalcoquine anisine derivative represented by the formula [r'] and a 4' N derivative represented by the formula [1■].
, N-disubstituted carbamoyl halide.

(1)--111--[V■] Above formula (IV
In LCVII3, Y is, for example, fluorine, chlorine, bromine,
Halogen such as iodine, R' is a lower alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, 5ec-butyl, tert-butyl, etc. For example, methquine, ethoxy, propochine,
Isopropoxy.

It represents a lower alkoxy group having 1 to 4 carbon atoms, such as butoxy, 5ec-butoxy, and te-10-butquine.

This reaction is based on acids such as benzene and toluene.

Hydrocarbons such as quinolene, ligroin, hexane, ether, isopropyl ether, tetrahydrofuran,
Ethers such as dioxane, ethylene glycol dimethyl ether, and methyl cellosolve; halogenated hydrocarbons such as chloroform, carbon tetrachloride, and dichloromethane;
It may be carried out in a solvent such as dimethylformamide, dimethylformoquine, acetonitrile, ethyl acetate, or the like. These solvents can be used alone or, if necessary, two or more solvents may be mixed in an appropriate ratio, for example, from 1:1 to 1:10. When a mixed solvent or the like is used and the mixed solvent is not a homogeneous phase, the reaction may be carried out in the presence of a phase transfer catalyst.

This reaction may be carried out in the presence of a deoxidizing agent, and suitable deoxidizing agents include, for example, alkali metal hydrogen carbonate (e.g., sodium hydrogen carbonate, potassium hydrogen carbonate), alkali metal carbonate (e.g., sodium, potassium carbonate, etc.)
, alkali metal hydroxide (e.g., potassium hydroxide, sodium hydroxide, etc.), trimethylamine, triethylamine, tributylamine, hemethylmorpholine, N
It is also possible to use inorganic and organic bases such as -methylpiperidine, N,N-dimethylaniline, pyridine, picoline, lutidine. The above organic base itself can also be used as a solvent.

Compound [IV] is usually used in a molar ratio of 1:1 to 1 historical compound [1''], but in some cases, one may be used in excess (for example, 1:5 to 5:1). You can also do it.

The reaction can usually be carried out under water cooling to about 120°C, preferably at a temperature of about 10 to 50°C. The reaction time can be set appropriately depending on the reaction temperature, but is in the range of several minutes to several tens of hours, preferably 0.5 to 8 hours.

Compound [1] can also be produced by bi-reacting carbonyl compound (V)1 with compound (1) and (Vl:).

, II7゜y-c-y (v) and ]1, y', y7-z halogen such as chlorine, bromine, iodine, nitrogen-containing aromatic group such as triazole, imidazole, benzotriazole, benzimidazole, pyrazole, etc. It represents a 5-membered ring group, and any number of lower alkyl groups such as phenyl, methyl, ethyl, and propyl may be substituted on the ring of the nitrogen-containing aromatic 5-membered ring group. R1 has the same meaning as above.

This carbonyl compound [■], compound [I”] and (vi
), for example, benzene, toluene.

The treatment is carried out in an inert organic solvent such as xylene, chloroform, acetonitrile, methylene chloride, tetrahydrofuran, acetone, ethyl acetate, dimethyl sulfoxide, dimethylacetamide, dimethylformamide, hexamethylphosphoramide, etc. alone or in a mixed bath medium. Ru. The reaction temperature is generally about -20° to 40°C, preferably about -1° to 20°C. The reaction usually proceeds quickly and is completed in about 0.5 to 3 hours. Typical reaction times are about 1-2 hours.

Compound [1"] for carbonyl compound [■].

It is preferable to use approximately equimolar amount of [V1], but from 1,1 to
There is no problem even if it is used about 2.0 times. In addition, this reaction may be carried out in the presence of a deoxidizing agent, and as a suitable deoxidizing agent,
For example triethylamine, tributylamine, N-methylpiperidine, N-methylmorpholine, N,N-dimethylaniline, pyridine.

Organic bases such as picoline, lutidine, collidine, etc., and inorganic bases such as alkali metal bicarbonates (eg, sodium bicarbonate, potassium bicarbonate), alkali metal carbonates (eg, sodium carbonate, potassium carbonate) may also be used.

The compound [■] thus obtained can be obtained by known means,
For example, a sushi, vacuum concentration, two fractional distillation.

Solvent extraction, liquid conversion, dissolution transfer, chromatography.

It can be isolated and purified by crystallization, recrystallization, etc.

The starting compounds C11) and (II) of the present invention are known compounds and can be easily prepared by methods described in various literatures.

The present invention will be explained in more detail below with reference to Examples, Test Examples, and Reference Examples.

Note that the symbols used in the examples have the following meanings.

S: Singlet, d: Doublet, t: Triblet, q: Cultite, m: Multiblet Example 1゜2-chloro-1-(2-(5-ethyl-2-pyridyl)
Etquin]-4-nitrobenzene (Compound No. 1) 2-(5-ethyl-2-pyridyl)ethanol 7.6 g
, 2-chloro-1-fluoro-4-nitrobenzenes,
8g, benzyltriethylammonium chloride 2.3#'
Dissolve 4 ml of powdered sodium hydroxide in dichloromethane and stir at 15 to 20 ''C.
．． Add 5g in 8 portions to 1o for 30 minutes. Further room/
After stirring for 2 hours at
Wash twice with water. Dry with anhydrous magnesium sulfate, concentrate, and recrystallize the obtained crystals from methanol to obtain the title compound 1.
2.8.9'r obtained. Melting point 88-89°C.

NMR (CDCl 8) δ, ppm; 1.18 (
8H,t.

7.54 (z, CH3), 2.55 (2H, Q.

J2'1.511z, (-H2), 8-09
(2H, t.

J-6,5Hz, CH2), 4. d 2 (2H
,t.

J = 6.5H2, CH2), 6.68-7.42 (8H
, m.

Aromatic j(), 7.80-8.80 (8H,m,
Aromatic h%H) Elemental analysis C15H16cl! Calculated value as N2o8 (%l:c, 58.78iH, 4,98;N
, 9.18 Actual value (%): C, 58,56; H, 5,0
9; N, 8.85 Example 2゜2-[2-(5-ethyl-2-pyridyl)ethoxy]5
~Nitrobeschizotocyfluoride (Compound No. 2) 2-(5-ethyl-2-pyridyl)-ethanol 7.6
g, 2-chloro-5-nitropenzotrifluoride 11
．． 8.9. Benzyltriethylammonium chloride 2.8
The title compound t4.
8g'& get. Melting point: 82°C.

NMR (Cl)C7?8)δ, pI)tn; 1.19
(81-1, t.

J-7,5Hz, (-Ha), 2.61 (2
H,t.

J = 7.51-17. ．． CH2), 125(2H
, t, J = 7.0°CH2), 4.52 (21
1,t, J=7,011z, C112).

6.95-7.59 (81-1, m, aromatic F,
8.20-8.58 (8H, m, aromatic II) Elemental analysis Calculated value as 016'''15N208FB (
@: C:, 56.47; H, 4, 44; N, 8.23 actual value (coefficient 1: c, 56.40; H, 4, 81; N, 8.
44 Example 3 2-chloro-1-(2-(5-ethyl-2-pyridyl)
Ethoxy]-4-nitrobenzene (compound number l) 2-(5-ethyl-2-pyridyl) in 4 oml of toluene
Ethanol 8.02!1.2-Chloro-1-fluoro-
4-nitrobenzene 4.85 E/ + 1 g of benzyltriethylammonium chloride and 50% aqueous sodium hydroxide solution 8.21"a:: were added, and after stirring at room temperature for 7 hours, 1.6.li'Y of water was added, Stir for an additional 6 hours. Add 50ml of toluene to the reaction mixture, and add 6L of water twice.
Fru.

After extracting twice with 2N hydrochloric acid, the hydrochloric acid layer is neutralized with sodium hydroxide, and extracted three times with chloroborum. After drying over anhydrous sulfuric acid and distilling off the solvent, the resulting crystals were recrystallized from methanol to obtain the title compound 4.6. Melting point 88-89°C.

Example 4 2-chloro-1-(2-(5-ethyl-2-pyridyl)
Ethoquino-4-nitrobenzene (compound number l) 2-(5-ethyl-2
-pyridyl)etha/-/Iz8.02 jp, 2-
Chloex'-t-fluoro-4-nitrobenzene 4.8
5y, potassium carbonate 2.8! ! , benzyltriethylammonium chloride lI was added and stirred at 100'C for 15 hours. After cooling, the reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off.

The residue was purified by silica gel column chromatography (solvent dichloromethane-ethyl acetate, 2:1),
8.68 gY of the title compound is obtained. Melting point 88-89°C0 Example 5゜2-chloro-1-(2-(6-methyl-2-pyridyl)
Ethoxy]-4-nitrobenzene (compound number 3) 2-(6-methyl-2-pyridyl)ethanol] 1.7
．． 9 and 2-chloro-1-fluoro-4-nitrobenzene 17.751% dry dimethylformamide 200+++
60% sodium hydride was added little by little over about 1.5 hours while stirring and cooling with water. After stirring for an additional 30 minutes, pour into 1.5 liters of cold water and collect the precipitated crystals.

The title compound 19.1 was obtained by recrystallizing this product from methanol.
9'a? obtain. Melting point: 91-92°C.

Table 1 shows the compounds represented by formula [I'] obtained by the same method as in Example 1.

US NMR (CDCeB) δ, ppm: 2.27 (8H,
s).

8.28 (2H, t), 4.48 (2H, t), 6.9
5-7.57 (sH, m), 8.00-8.42
(81-1,rn) Example 6゜4-(2-(5-7ethyl-2-pyridyl)ethoxy'
J-8-1 Lifluoromethylaniline (Compound Ichiyumi 13
) Method a) 2-(1-(5-ethyl-2-pyridyl)ethoxy J-
Dissolve 14.8 g of 5-nitropenzotrifluoride in 250 ml of ethanol, add 10% palladium, 1. f
1 was added thereto, and hydrogenation was carried out at room temperature and normal pressure.

After the reaction, the mixture was filtered with catalyst'x, and the solvent was distilled off under reduced pressure.The residue was dissolved in ethyl acetate and washed with water. After drying over anhydrous magnesium sulfate, 2 parts of the title compound 12.
Obtain 9gY. Melting point 47-49°c.

Colorless crystal.

Elemental analysis Total q value as C16I-11□N20F8 (
%l; C, 61,98; H, 5,52; N, 9.08
Actual value (%); C, 61,71i1-1.5.86;
8.75b method) 70 ml of water + 6.2 g of reduced iron and 1.5 g of concentrated hydrochloric acid
ml and stir at 50°C for 30 minutes. Then 2-(2-(5-ethyl-2-pyridyl)ethquine)
-5-Nitropencytrifluoride 12.5. ! i”a
:' Add and stir at 90-100°C for 2 hours. then 5
Cool to 0%C and add sodium bicarbonate powder 1.3
g and stir for 20 minutes. Cool the reaction solution to room temperature and filter the precipitate. The precipitate and Pa were extracted with chloroform, the chloroform layers were combined, washed with water, dried over anhydrous red sea bream sulfate, and concentrated to obtain the title compound 9.
8 g are obtained as crystals with a melting point of 47-49"C.

Compound [1] obtained in the same manner as in Example 5 a) is shown in Table 2 below.

(Hereinafter referred to as Koji) Test ji, Q, 'Example Antibacterial test compound against plant pathogenic bacteria (invention 11S compound numbers 11 and 12, control compound A (compound described in JP-A-139460) and b
(Chemical & Pharmaceutical Bulletin (CI+em, Pharrn.

J3ull, ) 3 0 volumes, a 5 so, 1 (
1 me of a predetermined concentration solution of 1982 H self-published compound] was taken into Veto J 11+1, and then 9 ml of dissolved potato agar medium was added and stirred uniformly.
'1) Crush and solidify.

Is it written in Table 8 on the front? 1. (At 111°11 [smear the octopus bacteria with a platinum looper, 28"C721f!j interval to 9
After culturing for 6 hours, the presence of bacterial growth) 11 is the minimum growth inhibitory concentration (M I
Find C). The results are summarized in Table 3.
-pyridyl)ethoxy)-a-trifluoromethylphenyl]urea 4-(2-(5-ethyl-2-pidzyl)ethkyne)-
a-Trifluoromethylaniline 1°6. ! 9beg 20m
A solution of 1 in dichloromethane? While stirring at 15-20 °C, 1,1-carbonyldiimidazole t,
o, p please add.

Stir this mixture for 20 minutes at 25-30"C.

Cool this solution to 15 to 20 tons, and stir for 50 minutes.
Gradually add 1.0 g of % dimethylamine aqueous solution. Add 1.0 g of % dimethylamine aqueous solution gradually.
Stir at c for 20 minutes. The reaction mixture is concentrated to dryness, and water is added to crystallize it. One crystal was taken, dried, and recrystallized from a mixed solvent of isopropyl ether and dichloromethane to obtain the title compound 1.8. ! ? 7a; Obtain.

Melting point 96-97"C0 colorless crystals.

Claims (1)

[Claims] [In the formula, R is a lower alkyl group, n is 1 or 2,
represents a halogen atom ligand or a lower haloalkyl group, and Z represents a nitro group or an amino group, or a salt thereof. [In the formula, R is a lower alkyl group, n represents 1 or 2] Compounds represented by the formula [In the formula, X represents a halogen atom or a lower haloalkyl group, and Y represents a halogen atom 7] A method for producing a compound represented by the formula [symbols in the formula have the same meanings as above], characterized by reacting with and in the presence of a base.