JPS59110672A - Urea derivative and its use - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I (R<1> is lower alkyl; n is 1 or 2; R<2> is halogen, or CF3; R<3> is R<1> or lower alkoxy) or its salt. EXAMPLE:N-{ 4-[2-( 5-Ethyl-2-pyridyl )ethoxy]-3-trifluoromethyl-phenyl }-N,N-dimethylurea. USE:A herbicide. Having high herbicidal activity, low phytotoxicity to crops such as wheat, etc. Preferably the content of an active ingredient in the herbicide is 10-90wt% in case of emulsion, wettable powder, etc., 0.1-10wt% in case of oil, dust, etc., and 1-20wt% in case of granule. PROCESS:For example, a pyridylalkoxyaniline derivative shown by the formula IIis reacted with an N,N-disubstituted carbamoyl halide shown by the formula III(X is halogen) in a solvent in the presence of a deoxidizer under cooling with ice or heating at <=120 deg.C for several minutes -tens hours to give a compound shown by the formula I or its salt.

Description

Detailed Description of the Invention The present invention is represented by the general formula CI) (wherein R1 is lower alkyl μ, n is 1 or 2°, R3 is lower alkyl or lower alkoxy, and R2 is halogen or trifluoromethyl). The present invention relates to compounds, salts thereof, methods for producing them, and herbicides containing the same.

Conventionally, example tld'N'-(3,4-dichlorophenyl)
-N,N-dimethylurea (diuron) and “-(4-(
Urea derivatives such as 4-chlorophenoxy)phenyl)-N,N-dimethylurea (chloroxuron) are known to have herbicidal activity, but the selectivity of their herbicidal activity between crops and weeds is unknown. Although this is not always sufficient, the development of a herbicide with high selectivity is still awaited.

In recent years, various studies have been carried out to improve this drawback, and some slightly improved compounds, such as those described in Patent Publication No. 56-13946 (), are now being obtained. However, these compounds also have poor herbicidal activity and crop safety. However, it is still not enough.

The present inventors aimed to further improve these points and find a high-state selective herbicide with even higher activity and less phytotoxicity.
As a result of continued research, it was found that compound CI) is a compound described in the above-mentioned patent publication No. 56-139640 that has a similar structure, such as N'
-(4-(3-(3-pyridi/L/)propoxy]phenylene/1z)-N,N-Dimethylurea has higher herbicidal activity than that, and has lower phytotoxicity to crops such as wheat, making it significantly more effective. After discovering that the present invention is superior, the present invention was completed after further various studies.

That is, the present invention provides (1) a compound represented by the general formula CI) and a compound represented by the general formula (2) (the symbols in the formula have the same meanings as above) and a compound represented by the general formula (in which R3 is (3) A method for producing a compound represented by the general formula [E] or a salt thereof, characterized by reacting the compound represented by the general formula [E] or a salt thereof with the compound represented by the general formula , Y each represents a halogen or a nitrogen-containing aromatic 5-membered ring group), a compound represented by the general formula (II), and a compound represented by the general formula (symbols in the formula have the same meanings as above) (4) A herbicide containing a compound represented by the general formula [■] or a salt thereof.

In the above general formulas (I) and (If), R1 is, for example, methyl, ethyl, propy/1-, isopropyl, buty/
1/, 8ea-butyl, tert-butyl and other lower alkyl yv)&, which may be substituted 1 to 2 at any position of the pyridine ring. R represents, for example, a halogen atom such as chlorine, bromine, iodine, or fluorine, or trifluoromethyl ivh'=.

In the above general formulas CI), (■), and (V), R3 is
For example, methyl, ethyl, propyl, isopropy/l/
lower alkyl groups such as Lt, Bee-butyl, t, ert-butyl, e.g. methoxy, ethoxy, propoxy, isopropoxy, butoxy, 5ec
Indicates lower alkoxy groups such as -butoxy, tert-butoxy, etc.

In the above general formula [■], Y represents, for example, a halogen such as chlorine, bromine, or boron, a nitrogen-containing aromatic 5-membered ring group such as triacy μ, imidazo μ, benzotriazole, benzimidazole, piracy μ, The five-membered nitrogen-containing aromatic ring may be substituted with any number of phenyl or lower alkyl groups such as methyl, ethyl, and propyl. Preferred specific examples of such compound (IV) include phosgene, 1,1'-force μbonyldi(1,2,4-)lyase/L'), 1,1'-
carbonyldiimidazole, 1,1'-carbonyldibenzotriazo-μ, 1,1'-force l/bonyldibenzimidazole, 1,1'-carbonylbis-
(3,5-dimethylpiracy3'), 1,1'-carbonyldipyrazole, 1,1'-carbonylbis-(
2-methylimidazo-/l/), 1,1'-carbonyldiindazo-/l/, 1,1'-polybis-(2-phenylimidazo-/I/), and the like.

Compounds of the present invention CI) include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, p-)/L/enesulfonic acid, formic acid, acetic acid, propionic acid, tartaric acid, malic acid, succinic acid,
It may also be an acid addition salt with an organic acid such as fumaric acid.

When using the compound CI) of the present invention as a herbicide,
Depending on the purpose of JII, an appropriate tt' is dissolved or dispersed in a compound (e.g., a solvent), and a suitable solid carrier (compound CI) is used.
If necessary, emulsifiers, suspending agents, spreading agents, penetrating agents, wetting agents, mucilage agents, stabilizers, etc. Additives, oils, emulsions.

Hydration: Used as All type, 9 grains, 9 tablets, spray, ointment, etc. These fabrications 1 can be completed by a method known per se.

The content ratio of the active ingredient in the herbicide varies depending on the purpose of use, but for emulsions, hydrating agents, etc., it is 10 to 90: +f
Approximately tf^% is appropriate, and 0 for oils, powders, etc.
．． Approximately 1 to 10% by weight is appropriate, and for granules it is 1 to 10% by weight.
Appropriately, it is about 20%, but these values may be changed as appropriate depending on the purpose of use.

In addition, when using emulsions, irrigation agents, etc., it is preferable to dilute and increase the amount (for example, 100 to 10,000 times) with water as appropriate.

Examples of liquid carriers (solvents) used in herbicides include water, alcohols/I's (e.g., ethyl alcohol, ethyl alcohol, ethylene glycol, etc.), ketones (e.g., acetone, methyl ethyl ketone, etc.), and ethers (e.g., dioxane, tetrahydrofone, cellosolve, etc.), aliphatic hydrocarbons (e.g. gasoline, kerosene, kerosene, fuel oil9 machine oil, etc.), aromatic hydrocarbons (e.g. benzene, toluene, xylene,
Solvent naphtha, methylnaphthalene, etc.), other halogenated hydrocarbons (e.g. chloroform, hydrogen tetrachloride, etc.), acid amides (e.g. dimethylformamide, etc.), esters (e.g. ethyl acetate, butyl acetate).

Suitable solvents include glycerin esters of fatty acids, nitriles (eg, acetonitrile, etc.), and one or a mixture of two or more of these may be used. As solid carriers (diluents, fillers), powders of vegetable origin (such as soybean flour, tobacco flour, wheat flour, wood flour, etc.), mineral powders (such as kaolin) are used.

Clays such as bentonite and acid clay, talcs such as talcum powder and waxite powder, silicas such as diatomaceous earth and mica powder, etc.) Furthermore, alumina, VFR: yellow powder, and activated ash are also used, and one or two of these are used. Use a mixture of more than one species.

As ointment bases, for example, polyethylene glycol, pectin, polyhydric alcohol esters of higher fatty acids such as glycerol ester/l' monostearate, cellulose derivatives such as methylcellulose, etc.
Sodium alginate.

Bentonite, higher alcohol, polyhydric alcohol such as glycerin, petrolatum, white petrolatum, liquid halafine, lard, various vegetable oils, wonorin, dehydrated lanolin,
One or more of hydrogenated oils, waxes, resins, etc., or those containing various surfactants and the like can be selected as appropriate.

'Surfactants used as emulsifiers, spreading agents, penetrating agents, dispersants, etc., may be used in soaps,
Polyoxyalkylaryl ester/I'm (e.g., Nonar μ■, manufactured by Takemoto Yushi 1), Alki/'f & Cm salts (e.g., Emarl 1o■, Emarl 4゜■, Kao Atlas II!l'l, A μ-kill sulfonates (e.g., Neogen ■, Neogen T ■, manufactured by Dai-Kogyo Seiyaku XI; Neoperex ■, Kao Atlas additional product), polyethylene glycol ether/l/types (e.g., Norpo/1'85■, Nonibor/ l'100■, Noni Ball 160■, Sanyo Kasei EL
), polyhydric alcohol esters (e.g. Tosheen 2o
■, Tween 8°■, Kao Atowosu [LfilM], etc. are used.

When compound CI) is used as a herbicide, the amount used is about 1 to 50 g, preferably about 2 g/are of field.
-401F, about 1 to 50 f1, preferably about 2 to 40 g, per 1 area of paddy field. Compound CI) is also suitable for use as a post-emergence treatment agent.

In addition, other types of herbicides,
Plant growth regulators, fungicides (e.g. organochlorine fungicides,
Organic sulfur fungicides, antibiotics, etc.), insecticides (organophosphorous insecticides, natural insecticides, etc.), l113 acaricides,
Nematicide, symbiotic agent, attractant, repellent y"+'l + pigment,
It can be used in combination with other ingredients such as Hi-sashi.

The α-product CI) of the present invention is produced, for example, by reacting the pyridylalkoxyaniline Ml R form represented by the general formula (IT) with the N,N-disubstituted carbamoyl hawide represented by the general formula E Iff). .

In the general formula (Ill) or for example fluorine + l'
Indicates halogens such as t+ elements, odors, and iodines.

This reaction is commonly performed with eg benzene, toluene.

Hydrocarbons such as xylene, ligroin, and hegisan a:N
, ether, isopropyl ether, hydrofuran, dioxane, ethylene glycol dimethyl ether, methyl cellosolve), halogenated hydrocarbons such as chloroform, carbon tetrachloride, methylene chloride, dimethylformamide, dimethyl sulfoxide, acetonitrile.

1! It may be carried out in a solvent such as ethyl.These solvents can be used alone, or if necessary, two or more kinds can be mixed in appropriate proportions, e.g. They may be mixed at a ratio of 1:1 to 1:10.

When a mixed solvent or the like is used and the mixed solvent is not homogeneous, the reaction may be carried out in the presence of a phase transfer catalyst.

The reaction may be carried out in the presence of a deoxidizing agent. Examples of deoxidizing agents include alkali metal hydrogen carbonates (sodium hydrogen carbonate,
Potassium hydrogen carbonate), alkali metal carbonate (sodium carbonate, potassium rehydrate, etc.), alkali metal hydroxide (potassium hydroxide, sodium hydroxide, etc.), trimethylamine,
Inorganic and organic salts such as triethylamine, tributylamine, N-methylmorpholine, N-methylpiperidine, N,N-dimethylaniline, pyridine, picoline, /I/tidine, etc. can also be used. It can also be used as a solvent itself.

The compound (III) is usually used in a molar ratio of 1:1 to the starting material compound (TI), but in some cases, one of the starting materials can be used in excess (for example, 1:5 to 5:l). Ru.

The reaction is usually carried out under water cooling to 120°C, preferably 10°C.
It can be carried out in one grade at ~50°C.

The reaction time can be appropriately set in relation to the reaction height, but is in the range of several minutes to several tens of hours, preferably 5 to 3 hours.

In addition, the present compound CI) is a carbonyl compound (TV
) and the compound Cll) and (V).

The reaction between carbonyl compound (JV), compound C [) and [■] can be carried out using, for example, Ll:, benzene, toluene, xylene,
The reaction is carried out in an inert organic solvent such as chloroform, acetonitrile, methylene chloride, tetrahydrofuran, acetone, rit=Ne ethyl, dimethylsufi/phoxite, dimethylacetamide, dimethylformamide, hexamethylphosphoramide, etc. alone or in a mixture thereof. The reaction temperature is generally -20 to 40°C, but
-10 to 201S is preferable. The reaction usually proceeds quickly and is complete between about 0.5 and 311ζY. Typical reaction times are 1 to 2 hours.

Compound [■] for carbonyl compound (IV').

It is preferable to use approximately equimolar amount of [v], but 161 to 2
, it is okay to use about 0 times. The reaction may also be carried out in the presence of a deoxidizing agent, such as triethylamine or tributylamine.

N-methylpiperidine, N-methylmorpholine.

Organic bases such as N,N-dimethylaniline, pyridine, picoline, lutidine, collidine, etc., such as #oxygen alkali metals (e.g., sodium bicarbonate, potassium bicarbonate), alkali metal carbonates (e.g., sodium carbonate, potassium carbonate), etc. P-free bases may also be used.

In addition, in this reaction, first (ID
and (IV) react to form a compound represented by the general formula (VI) (the symbols in the formula have the same meanings as above) or/and a compound represented by the general formula [■] (the symbols in the formula have the same meanings as above) Then, (V) reacts with these [■] and [■] to generate CI), so (, VT ) and [■
] may be performed in isolation.

In addition to the above-mentioned method, the compound [I] or a salt thereof of the present invention can also be produced, for example, by the following method.

That is, N'-(3-substituted-4-(2-(2-pyridyl)
v) Ethoxy A pheni/l/-N-hydroxyurea M
This method uses a methylation reaction of a conductor. Examples of methylating agents include methyl borate, dimethyl sulfate, and para-toluenesulfonic acid methyl ester.

The reaction is benzene, toluene, xylene, methanol, ethanol, isopropanol, diethyl ether, tetrahydrofuran, dioxane, dimethylformamide,
The reaction can be carried out in an organic solvent such as dimethyl sulfoxide, dichlormechne, or chloroform, or in water or a mixed solvent thereof. Further, the reaction may be carried out in the presence of a deoxidizing agent, and the reaction is easily carried out using an organic base such as pyridine or an inorganic base such as potassium carbonate, sodium hydroxide, potassium hydroxide, etc. as the deoxidizing agent. It will be done. The reaction is carried out under cooling, at room temperature, or by heating. The reaction time varies depending on the reaction temperature and the type of reagent used, but is about 0.5 to 10 hours.

Furthermore, compounds represented by the general formula (IX) (wherein z represents a halogen atom, alkylsulfonyloxy or allylsulfonyloxy (or phenylsulfonyloxy), L/, Rlfnij: the same meaning as above) and general The target compound CI) can also be obtained by reacting with a compound represented by the formula () (in the formula, R2, R3g<the same meanings as above).
can be obtained. The reaction is benzene.

Toluene, xylene, diethyl ether, tetrahydrofuran, dimexane, chloroform, carbon tetrachloride, ethyl acetate, methanol, ethanol.

Organic solvents such as isopropanol, dimethyl sulfoxide, N-methylformamide, or water, etc.
Deoxidation of pyridine, triethylamine, sodium hydroxide, water 1') potassium carbonate * r#[j4 sodium etc.
can be carried out in the presence of The reaction is carried out under cooling, at room temperature, or under heating, and depending on the reaction time, reaction 61
It varies depending on the degree and the type of reagent used, but it is 0.5 to 1
It takes about 0 hours.

The salt of the compound CI)J thus obtained is:
Known means such as concentration, vacuum concentration.

It can be isolated and purified by one-fraction distillation, solvent extraction, liquid conversion, dissolution, chromatography, crystallization, recrystallization, etc.

When compound [■] is obtained in the form of a free base, it can be converted into the above-mentioned salt, and when compound CI) is obtained in the form of a salt, it can be converted into the free base according to methods known per se.

Compound (TI) used as a raw material in the method of the present invention
& soil can be manufactured by the following manufacturing method.

A preferred raw material production method is summarized in the following reaction formula.

2 [M] [Sword ■] ○Plate] (II) The first step is to react the compound of general formula (XI) with the compound of general formula [X] in the presence of a base. For example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide (9) are hydrogenated to alkali metal carbonates (F, such as sodium carbonate, potassium carbonate, etc.)
Inorganic bases such as +1 um are preferred. It may also be a mixed base such as soda lime.

This reaction includes hydrocarbons such as benzene, toluene, xylene, hexane, ligroin, ethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, chloroform, carbon tetrachloride, etc. Hydrogen halides such as methylene chloride, amides such as dimethylformamide, dimethylamide, and N-methylpyrrolidone.

It may be carried out in a solvent such as dimethyl sulfoxide, sulfolane, acetonitrile or the like. These solvents can be used alone, or two or more of them can be used as a mixture in an appropriate ratio, if necessary.

The bases used in reactions using these solvents do not dissolve sparingly in these organic solvents, so the reaction system is often a two-phase system, such as 4R ammonium compounds, quaternary phosphonium compounds, etc. The reaction can be accelerated by adding a phase transfer catalyst such as.

Moreover, this reaction can also be carried out by a liquid-liquid two-phase reaction between an aqueous solution of a base and an organic solvent. In this case as well, the reaction can be promoted and carried out advantageously by adding a phase transfer catalyst.

The starting compounds [M] and [X] are usually used in a molar ratio close to 1:1, but in some cases one may be used in large excess.

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 (xi) and base used, the solvent, etc.

The second step is carried out by reducing the thus-produced compound (0) according to a method known per se.

For example, the nitro compound (X, [) is ethanol.

Ethyl acetate/l/ #P Reduction using sodium sulfide and dorazine in an organic solvent, water, or a mixed solvent thereof, reduction with iron, tin, etc. in the presence of an acid, or reduction with a catalyst such as platinum dioxide or palladium. It can be obtained by hydrogenation. What is the reaction?

It is carried out at 0 to 150 tons under normal pressure or increased pressure. After the reaction is completed, the target compound is obtained from the reaction mixture according to a conventional method.

The present invention will be explained in more detail with reference to fog examples, test examples, and examples below.

Note that the symbols used in Reference Examples, Examples, etc. have the following meanings.

81 singlet, d, doublet t.

Triplet, m, multiplet reference example/2-(5-ethyl/l/-2-viridi/l/) ethanol-μ
7.69. Dissolve 8-8 g of 2-chloro-1-fluoro-4-nitrobenzene + 23 g of benzyltriethylammonium 'f Add 4.5 g of sodium in 3 portions every 30 minutes. After further stirring at room temperature for 2 hours, the reaction solution is filtered and the P solution is washed with water. Dry over anhydrous magnesium sulfate and concentrate to obtain the solution. The obtained crystals were recrystallized from methanol-μ to give 2-chloro-1(2
12.89 of -(5-ethyl/I/-2-pyridi/I/)ethoxycou-4-nitrobenzene are obtained. Melting point 88-89
t.

N M R (eDc13) δI) pm+ 1.18 (
3H,t,;r=7.5HZ,CH3) -2-55
(2H, q + J = 7.5 HZ T CH2)
+3.09 (2H, t = J = 6.5 Hz,'
CH2), 4.32 (2H, t, J-6,5Hz
, CH2), 6.68 7.42 (3H, m.

ph-H & py-H), 7.80-8.30 (
31 (,m, ph-H&py-H) Elemental analysis Calculated value as C15H15CIN203 (@
; C58,73; H4,93+ y 9.13 actual value) i C58,56i H5,09i N 8.
85 Reference Example λ 2-(5-ethy/l/-2-pyridi/L/)-ethano-IL"1.6f, 2-chloro-5 in the same manner as Reference Example/
-11.3 g of nitrobenzotrifluoride, 2.39 g of benzyltriethylammonium chloride, 1-(2-(
14.8 g of 5-ethy#-2-pyridi/I/)ethoxy]-5-nitrobenzotrifluoride are obtained.

r71d1 point 82.

NMR(CDCl2)δppm; H9(3n,t
, J=7sHz, CH3), 2.61(2H, q
,,T=7.5H2, CH8).

3.25 (2H, t, J=7.0H2, CH2),
4.52 (2H.

t, J=7.0Hz, CH2), 6.95 7.59(
3B, m.

ph-H & py H), 8.20-8.53 (3H
, m, ph-H & py-H) Elemental analysis Calculated value 1@ as C□6H15N203”3
: C56,47NH4,44i N 8.23 Actual 7 Rules 1): c 56.40; H4,31;
N 8.44 Reference Example 3 2-(5-Methyl/l/-2-viridi/L/)ethano-A/3,029,2-chloro-1-fluoro-4'-nitrobenzene 4 in 40 liters of toluene .85 f, 1 g of benzyltriethylammonium chloride and 3.2 g of a 50% IJ hydroxide aqueous solution are added and stirred at room temperature for 7 hours, then 1.6 g of water is added and stirred for an additional 6 hours. Add 50 ft of toluene to the reaction mixture and wash twice with water. After the organic layer is extracted twice with 2N hydrochloric acid, the hydrochloric acid layer is neutralized with sodium hydroxide and extracted three times with chloroform. It was dried over anhydrous magnesium sulfate, the solvent was distilled off, and the obtained crystals were recrystallized from methanol to give 2-chloro-1-
Obtain 4.68 g of [2-(5-methy/l/-2-viridi/I/)ethoxycou-4-nitrobenzene. Melting point 88~
89u0 Reference Example 2-(5-methy/l/
-2-pyridi/L/) ethanol/1/3.02g, 2-
Chloro-1-fluoro-4-nitrobenzene 4.85q
, 2.8f of potassium carbonate, and 1g of benzyltriethylammonium chloride were added, and 100t! Stir for 15 hours. After cooling, the reaction mixture was poured into water and extracted with ethyl acetate. The organic layer is washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent is distilled off. Remove the residue
It was purified by column chromatography (solvent dichloromethane-ethyl acetate, 2:1), and 2-chloro-1-(
3.68 f of 2-(5-methy/l/-2-viridi/l/)ethoxycou-4-nitrobenzene are obtained. Melting point 88-8
9C Reference example 2-(6-methyA/-2-pyridyl)ethanol 13.
Dry 177 g of 71F and 2-chloro-1-fluoro-4-nitrobenzene; 200 g of 1'Q dimethylformamide.
ml, add 5 g of 60% water-accumulated sodium little by little while stirring in water over about 1.5 hours.

After stirring for an additional 30 minutes, pour into cold water of 1.5e to remove precipitated crystals. This was recrystallized from methanol and 2-chloro-1-(2-(6-methyl-2-bilyS/
lv) 19.89 of ethoxycou-4-nitrobenzene are obtained. L: Green point: 91-92°C The following compounds were produced in the same manner as in this reference example.

Table 3-CH3C1121-122 4-CH3C189-90 5 CH3Cl*4.6-((H3)2 (1105-1064-CH
3cps 106-1086-CH3ci'3
83~854.6-(CH3>2ay'379~8
16-CH3F'72~74 5-02H5F' 50* N M R
(CDC13) δppm: 2.27 (3H, s)
.

3.28 (2H, t), 4.48 (21 (, t), 6.
95-7.57 (3H, In), 8.00-8.42 (
3H, m) Reference example Otsu 2-(2-(5-methy/l/-2-pyridiμ)ethoxycou-5-nitrobenzotrifluoride 148Q was dissolved in ethanol-/I'250*/ and 10% palladium on carbon was added. 1
．． 59 was added and hydrogenated at room temperature and pressure.

After the reaction, the catalyst was removed from the oven and the solvent was distilled off under reduced pressure, and the residue was dissolved in dimethyl acetate and washed with water. Anhydrous sulfur + 'l'2
After drying with magnesium and compressing under reduced pressure, 4-C
12.9 g of 2-(5-ethyl//-2-pyridi/I/)ethoxy-3-trifluoromethylaniline are obtained. Melting point: 47-49°C, colorless crystals.

Elemental analysis Total I'll as C16H□7N20F'3
f direct (@: C61,93; H5,52i
N 9.03 actual measurement value (@: c 61.71i H
5,36; Ns, 75 steps dorsal side 7 2-chloro-1-(2-(6-methyl-2-pyridi/I
/) Ethoxy-4-nitrobenzene is,.

9 was dissolved in ethanol (101) tql, 1.5 g of baladium carbon (10%, manufactured by Mitsuwa Chemicals) was added and subjected to contact AL. After the reaction was completed, the baladium dihydrogen was evaporated and the :F3 solution was concentrated to dryness.
-C2-C6-methy/L'-2-pyridyl)ethoxy]
Get aniline. Melting point: 63-64°C, colorless crystals.

NMR (CDCl2) δpP”i 2.48 (s
,3H) ,3.15(,t,2H),3.40(a,
2H), 4.22(t, 2H).

6.21-7.18 (m, 6E1) Elemental analysis value Calculated value as C engineering 4H engineering, ClN2O (@
: C64,00+ H5,759N 10.66 Actual value (C63,78 line H5,92i N 10.9
1 Example/4-C2-<5-:x, CH/l/-2-pyridi/l/)
ff:)xy)-3-)lifluoromethylaniline1.
A solution of 6 g dissolved in 20 m/dichloromethane
Add 1,1'-carponiμ diimidazole lv1, Og while stirring at 20°C. Add this mixture to 25-3
Stir for 20 minutes at 0'C. This solution was heated at 15-20℃.
Cool and stir while adding 50% dimethylamine aqueous solution 1. Gradually add Og. The mixture is stirred under the same conditions for 10 minutes and at 25-30 tE for 20 minutes. The reaction solution is concentrated to dryness and crystallized by adding ice water. After drying the crystals,
Recrystallized from a mixed solvent of isopropyl ether and dichloromethane, N-(4-1-(5-ethyl A/2-viridi/
L/)ethoxy)-3-)lifluoromethylphenylene)
1.3q of -r,y-dimethylurea (compound number 3) is obtained. 4. 'i'll, temperature 96-97℃, colorless crystal N
MR(CI)C13)δPpm; 1.12(5,3
H).

2.46((1,21(), Z77(s, 6HL3.
00(t.

28), 4.20 (t, 2H), 6.36-7.40
(m, 6H).

7.98-8.18 (m, IH) Original base analysis value
C engineering 9”22”3N302 calculated value (@: c 59.
83+ Hs, 81i N 11.02 Actual value (Feed:
C59,31〼 El 5.67i N 10
．． 70 Example 4-C2-C5-ethy/L'-2-viridiIL/)ethoxy)-3-)/l/fluoromethylaniline 1.6 g
A solution of 20 m/dichloromethane
Add 1,1'-carbonyldiimidazo/1/1.09 while stirring at tE. Add this mixture to 25-30
Stir on the stove for 20 minutes. This solution is cooled to 15-20°C, and 0.3 g of methoxymethylamine is added while stirring. This mixture was heated under the same conditions for 10 minutes at 25-3()℃.
Stir for 20 minutes.

The 1zo reaction solution is concentrated to dryness and crystallized by adding ice water.

After drying, the crystals were recrystallized from carbon tetrachloride to form N-(4-(
2-(5-ethyA/-2-pyridyl)ethoxy)-3-
) 1.69% of phosphoromethyphenyl iN'-methoxy-W-methylurea (compound no. 4) is obtained. Melting point 68
-69°C, colorless crystals.

NMR (CDC13) δpp cap t, 1z (t, 3H)
, 249 (q+21.3.01 (s, 3g), 3.08
(t, 2H).

3.54 (s, 3H), 4.18 (t, 2H), 6.5
0-7.45 (m, 5H), 7.63 (s, LH), 8
．． 0O-8,18 (m.

IH) Elemental analysis value Cg H22F 3 N 303 words 1 calculation value (@: C57,42i H5,58+ N 10.
57 actual measurement value (L:A: C57,56i H5,50i
N 10.63 Example 3 4-(2-(5-4ti/L/-2-pyridi/v))xicy 3-fluoroaniline 2. Og and pyridine 2ON
After adding 2.0 g of dimethylcarbamoyl chloride to a homogeneous solution of / at room temperature, the mixture was stirred at 40 tons for 1 hour. After the reaction, extract with ethyl acetate and wash with water. After drying over anhydrous magnesium sulfate, the crude product obtained by concentration was recrystallized from carbon tetrachloride to obtain 1.59 N-(4-(2-(5-ethyl-2-
pyridi/1/) ethoxycy-3-fluorophene/l/
)-N',N'-dimethylurea (compound number 5) is obtained. 1 point 147-9°C, colorless crystals.

NMR (CDCl2) δppm; 1.18 (t, 3
H), 2.57 (q, 2H), 2.88 (s, 671)
, 3.14(t, 2H).

4.23 (t, 2H), 6.53 (s, IH), 6.6
3-7.47 (m, 5H), 8.25 (d, IH) Elemental analysis value C. H22F'N302 total η value (9:
C65-24i H6,69i N 12.68 actual value (@: C64,89; H6,72; N 12.
41 Example Rijiume fnl, / 2. (l of 4-[2-(
6-Methyl/L'-2-pyridi/I/)ethoxycou 3-
1.79 N-(3-fluoro-
4-(2-(6-methyfi/-2-pyridi1v)ethoxy]pheni/L/) -N',N'-dimethylurea (
Compound No. 11) is obtained. One point 167-1681m:
.

21! (Colored crystals.

NMR (CDCl2) δppm; 2.45 (s
, 3H) , 2.90(s, 61.313(t, zH
), 4.26 (t, 2a).

6.46 (s, IH), 6.69-7.52 (m, 6H
) Elemental analysis value C□7■1. . FN302 calculated value (→:
c 64.34; H6,35; N 13.24 dormitory measurement (@: C64,22+ H6,22i N 13
．． 17 Example 4-(2-(6-methy/L/-2-pyridyl→ethoxy')
1.7 g of [C]-3-fluoroaniline is dissolved in 30 ml of toluene, cooled at 5 to 10°C, and 6.4 q (t 5.8%) of phosgene (toluene solution) is added while stirring. The mixture is gradually warmed and heated to reflux for 1 hour.

After concentrating the reaction solution, 30M/toluene was added again to 15~2
Cool to 0°C and add 0.59% of methoxymethylamine.

This mixture was heated under the same conditions for 10 minutes at 25-30"C for 20 minutes.
Stir for a minute. The reaction solution is reduced to dryness and crystallized by adding ice water. After drying, the obtained crystals were recrystallized from carbon tetrachloride to obtain 1.2 g of N-(3-fluoro-4-(2-(6
-Methyl-2-pyridi~)ethoxy]pheni~) N
/-MeFxyW-methyμurea (compound number 12)? l+ru. Melting point 1] 0-111°C, colorless crystals.

NMR (CDCl2) δppm1 2.43 (8, 3
)1), 3.05(s, 311), 3.12(t,
2H), 3.57(s, 3H).

4.27 (t, 2H), 6.59-γ49 (m, 6H)
, 7.68 (8, lH) Elemental analysis value C17H20F'N303 calculation 6u (@
'C61,25;H6-05; W 12-60 actual value (to) l: C61,16; H6,'04i N
12.53 The following operations were carried out in the same manner as in Example 2 to obtain the compounds shown in Table 2.

81'G 2 tables] 5-=F; t cl Me 158-1
592 5-Fat, CI OMe 101~
1023 5-Et CF'3 Me 96~
974 5-Jt CF3 QMe 68~6
95 5-Jt F Me 147-1496
5-Et ]' OMe 83-857 6
-MeCI Me 111~1128G-uec]
, α(e66-679 5-MeCF3'Me
99N10110 6-M (3CF3 OMe
93～9612 6-Me F OMe
11ON11113 5-Me CI
Me 161-16214 5-Me C
I OMe 10')"11115 2.4-
DiMe CI Me 142-14516
2.4-DiMe CI OMe 135
~13717 2.4-DiMe CF3 M
e 113-11518 2.4 DiMe
CF3 OMe 104-10619 3-Me
CI Me 185-186203-
MeC1oMe15o~15221 4-B4e
CIMe 167-16822 4-Me
CF'3 Me 157-160 Example compound number (2) 25g, polyoxyethylene aryl ether surfactant 59. Thoroughly crush and mix 7 liters of talc to make an irrigation agent.

Example Z Compound No. (2) (10"), polyethylene glycol ether μ-based surfactant (20f), and cyclohexanone (71) were thoroughly mixed to form an emulsion.

Examples and Compound No. (3) sq, 40 g of bentonite, clay 509, and 5 g of sodium ligninsulfonate are thoroughly ground and mixed, water is added, the mixture is thoroughly kneaded, and the mixture is granulated and dried to obtain granules.

3 g of Example Compound No. (4) and 97 g of clay were thoroughly ground and mixed to form a powder.

Test Example 1 Fill a 10cm diameter Sihui pot■ with Sunagawa, and add Aobiyu, Pigweed, Pigweed, and Pigweed.

Separately sow white sagebrush, morning glory and corn, and inoculate 0.5. After covering with soil to a thickness of cm, the plants were cultivated in a greenhouse for 2 to 3 weeks, and when the plants reached the two-leaf stage, the following chemical solutions were applied to the leaves and foliage using a spray gun from above the plants. Two weeks after the chemical treatment, the phytotoxicity and herbicidal effects of each compound were evaluated according to the following criteria.

The chemical solution is to apply 1% (W) surfactant Twin 20■ to the specified ridge.
/W) in acetone IM/, diluted with deionized water to make a total volume of 7.5 tsl, and stirred the chemical solution using ultrasound.

The herbicidal effect is expressed using the following index.

Phytotoxicity to crops is expressed using the following index.

(However, indexes of 0 and 1 for crops mean that it is practical for crops.) The results are shown in the third column.

Third coat (compound in pair 11: JP 56-139460) Essay example λ Fill a sandy loam soil in a 10 cm diameter Sihui pot ■, sow pigweed, wild mustard, chickweed, and wheat separately. After covering the plants with soil to a thickness of 2 to 3 weeks, the plants were cultivated in a phylon house for 2 to 3 weeks, and when the plants reached the 2-leaf stage, a chemical solution containing a prescribed nail agent was applied to the stems and leaves from above the plants using a spray gun, as in Test Example 1. Treated. Drug treatment 3
After a week, the phytotoxicity and herbicidal effects of each compound were evaluated using the same criteria as Test Example Z.

The method for preparing the drug solution is the same as in Test Example. The results are shown in Table 4.

(Unexamined Japanese Patent Publication No. 139460) -583-

Claims (1)

[Claims] 1. General formula (in the formula, R1 is alkyl, n is 1 and 2°R2
hahalogen or trifluoromethyl, R is lower alkyl/
1/ or lower alkoxy) or a salt thereof. 2 Compounds represented by the general formula (wherein, R1 is lower alkyl, n is 1 or 2°, R2 is halogen or trifluoromethyl/L/, and R is lower alkyl or lower alkoxy) and also contain salts thereof. Herbicide.