WO1994007857A1

WO1994007857A1 - Cyclic amide compound and herbicide

Info

Publication number: WO1994007857A1
Application number: PCT/JP1993/001406
Authority: WO
Inventors: Yasuo Kawamura; Eiichi Oya; Kaoru Itoh; Hiroshi Kita; Hisashi Nakata; Kanji Sawada; Jun Satow; Tsutomu Nawamaki; Shigeomi Watanabe; Kimihiro Ishikawa; Yoichi Ito
Original assignee: Nissan Chemical Industries, Ltd.
Priority date: 1992-10-05
Filing date: 1993-10-01
Publication date: 1994-04-14
Also published as: AU4834693A; JPH06172306A; CN1085218A

Abstract

A cyclic amide compound represented by general formula (1-A) or (1-B), and a herbicide containing the same. In the formulae (1-A) and (1-B), R?1, R2 and R3¿ represent each hydrogen or alkyl; X represents oxygen or sulfur; Y represents halogen, alkyl, etc.; m represents an integer of 0 to 5; n represents 1 or 2; Q represents a heterocycle, naphthyl, fused heterocycle, etc.; and Q' represents phenyl, heterocycle, naphthyl, fused heterocycle, etc.

Description

— —

Ming TO cyclic amide compounds and herbicides

[Industrial applications]

The present invention relates to a novel cyclic amide compound and a selective herbicide containing the compound as an active ingredient.

[Conventional technologies and issues]

In recent years, with increasing global population, it is clear that the productivity of important crops will affect the food economy of each country. With these changes, it is inevitable that traditional agricultural forms will change toward the 21st century. In fact, it is increasingly necessary for farmers to develop herbicides that can economically and efficiently kill or control weeds that hinder crop cultivation. It is.

The development of such a herbicide with the following conditions is eagerly awaited.

It has a high herbicidal effect at low doses (especially from the viewpoint of environmental protection, it is necessary to kill weeds by spraying at low doses). It has a moderate residual effect. (In recent years, it has been a problem that drugs with long soil residues may damage later crops. — —

It is important to show a moderate residual effect. ), But quickly kills weeds after spraying (sowing and transplanting of the next crop is possible in a short period of time after treatment with chemicals); It is important to reduce the number of frequent weed control operations for those who have difficulty in controlling the weeds.), But also for a wide range of weed control targets (such as broadleaf weeds, grass weeds, perennial weeds, etc.). For weed species with different properties, an agent that can control these with one agent is desired.), And many applications (soil treatment effect, foliage treatment effect) In addition, a stronger herbicidal effect can be obtained by having both of these properties.), And those that do not show the phytotoxicity that poses a problem to crops (crop and weeds are mixed). Preference is given to those that can selectively kill only weeds in arable land.) Is desired. However, existing herbicides do not meet all of these requirements.

On the other hand, specific cyclic amide compounds are known, for example, JP-A-54-7Q2, JP-A-2-1-1, and European Patent Publication No. 2586. , U.S. Patent No. 722 ', U.S. Patent No. 50215, Belgian Patent Application, Tetrahedron Lett., 28 (6) , 613-616 (1987), Chemistry Letters

(11), 1943-1946 (1984) ^ Journal of O.A.G., Chemistry (]. Or.Che πι, 48 (22), 4058-4067 ( 1983) And so on.

[Means for solving the problem]

In view of such a situation, the present inventors have shown selectivity for important crops, have an excellent herbicidal effect at a low drug dose on many weeds, and As a result of continuing research to develop a herbicide having a foliage treatment effect, the formula (111A) or the formula (111B)

(11-A) (1-B)

[In the formula, R ¹ , R ^L and R ^{独立 each} independently represent a hydrogen atom or a ~ c ₄ alkyl group, X represents an oxygen atom or a sulfur atom, γ Ha b gain down atoms, ~ c ₄ a Ruki group, a _C} ~ C a Le co key sheet group CC Nono b a Noreki Le group or the C i ~ c ₄ c b a Le co key sheet group And m represents an integer from 0 to 5, and if m is an integer from 2 to 5, Y may be the same or different. n represents 1 or 2, and Q represents an optionally substituted heterocyclic ring, an optionally substituted naphthalene ring, or an optionally substituted It was condensed heterocyclic shea § cyano group or C 0 ₂ A (A is a hydrogen atom, CC ^ A Le key Le Represents one group or a phenyl group. And Q ′ is an optionally substituted phenyl ring, an optionally substituted heterocyclic ring, an optionally substituted naphthalene ring, I substituted contracted if heterocycle, (the a represents. the same as defined above) C 0 ₂ a was or shea § cyano group represents a. (Hereinafter, referred to as the compound of the present invention) represented by the following formula:

A good Q is

Zb

O

Zb

N ヽ / N

Be overwhelmed

A good Q '

Be obscured

Next, the replacement group is concretely added.

R ¹ represents a hydrogen atom, a methyl group, an ethyl group, or n-propyl

1 S 0 propyl group n butyl group so — butyl group sec 1 butyl group and ter butyl group are exposed, preferably hydrogen atom, methyl The radicals and the ethyl radicals are exposed, more preferably the methyl and the ethyl radicals are exposed.

R ² is a hydrogen atom, a methyl group, an ethyl group, n—propyl group, is 0—propyl group, n—butyl group, is 0—butyl Group, sec-butyl and tert-butyl groups, preferably hydrogen atoms, methyl and ethyl groups, and so on. More preferably, a methyl group and an ethyl group are provided.

R ³ is a hydrogen atom, a methyl group, an ethyl group, n—propyl group, iso—propyl group, n—butyl group, iso—butyl group, sec Both butyl and terbutyl groups are exposed and are preferred. Or a hydrogen atom, a methyl group or an ethyl group.

Y is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, n-propyl group, iso-propyl group, n-petit atom Butyl, iso—butyl, sec—butyl, tert—butyl, methoxy, ethoxy, n—propoxy, iso—propo Xyl group, n — butoxy group, iso — butoxy group, sec — butoxy group, tert — butoxy group, difluoromethyl group, triphenyl Olemethyl group, chloromethyl group, bromomethyl group Pentafluoro group, 2 — chloromethyl group, difluoro group Toxi group, Trif ole oxime group, 2, 2, 2 — Trifluoro mouth ethoxy group, 2 — Cyclo mouth ethoxy group and 3 — Black mouth Proboxy groups are exposed, and are preferably fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group, ethyl group, and trifluoromethyl. Group, diphenyl olemethyl group, chloromethyl group, methoxy group, ethoxy group, diphenyl olemethoxy group and trifl The base is exaggerated.

X is an oxygen atom and a sulfur atom.

m represents an integer of 0 to 5, and when m is an integer of 2 to 5 and Y is the same or different, Y may be the same or different.

n represents 1 or 2. o 1 H

i end

'

, Ding '

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N ^: "

N 1 »

V m

It m m m w

5 O m

/ i £ 6 / dfJDd Q

Zb

b

Dimension lo / £ 6df / Jo-d Kasumi S.6 Dimension OAV

AV

90riO / £ 6df / JOd s S8 O

and

Is irritated,

Q 'represents cyano, carboxy, methoxycarbonyl, ethoxycarbonyl, n-propoxy Nil group, io — Propoxy carbonyl group n Butoxy carbonyl group

1 s butoxy carbonyl group, Sec 1 butoxy carbonyl group e rt — Butoxy bonole group, phenoxy carbonyl group,

NRI 4 -Za

z NRI

o // tl £ 6drh> /d.S80

0 / Dimensions 6 ο

-

and

Is irritated,

The substituent z is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, n-propyl group, iso-propyl group, n-butyl , Is 0 —butyl group, sec —butyl group, tert —butyl group, methoxy group, ethoxy group, n —propoxy group, iso —pro Pox group, n — butoxy group, iso — butoxy group, sec — plastic, ter butoxy, difluoromethyl, trif Chloromethyl group, chloromethyl group, bromomethyl group, phenyl chloromethyl group, 2 — chloromethyl group, dichloromethyl group Roxy meter base, trifluorometer base, 2, 2, 2 — Trifluoroethoxy group, 2 — Cross mouth outlet group, 3 — Gro mouth Si group, methylthio group, ethylthio group, n — propylthio group, iso — propylthio group, n — butylthio group, iso — petitio Norecho group, sec — Petitnorecho group, tert — Petithio group, Methynoresulfinyl group, Ethylosenofininole group, n — Nores fininol, iso — propyl fininol, n — butylinfinyl, iso — butylinfinin, sec — Butinosolefinyl group, tert — Butylsulfinyl group, Methyloneshonolehonyl group, Ethylsulhoninole group, n—Propi Le sulfonyl group, is 0 — propyl sulfonyl group, n — butinole Sulfonyl group, iso —butylsulfonyl group, sec—butylsulfonyl group, tert-butylsulfonylhonyl group, nitro group, metha X-carbonyl group, ethoxy-carbonyl group, n—Propoxy-carbonyl group, is 0—Pro-oxy-carbonyl group, n — Putoxycarbonyl group, is 0 — Butoxycarbonyl group, sec — Butoxybonyl group, ter Butoxy group , Carboxyl group and holmyl group, etc.

R ⁴ represents a hydrogen atom, a methyl group, an ethyl group, n—propyl group, is 0—propyl group, II—butyl group, iso—butyl group , Sec — The compound of the present invention having a butyl group and a terbutyl group is used as a herbicide for upland fields, paddy fields, and non-cultivated lands. It can be used in any of the processing methods.

The target weeds as the herbicides of the compound of the present invention include wild solgum, oaksakibi, johnsongrass, inubie, mexisino Grass weeds such as oak grass, ohisiba, enocologusa, suzumenotetsubo, etc .;モカダダモモダモダダダダモダモモモダモモダモダダダダダダダダモダモMouth, Kikashidasa, Tainubie, etc. are exposed.

The compounds of the present invention are important crops such as wheat, corn, barley, Contains compounds that can be used safely in soybeans, rice, cotton, beats, solgum, etc.

The compound of the present invention is also useful as a defoliant (defo1iant).

The compound of the present invention can be synthesized, for example, by the methods shown in the following schemes 1 to 3. (R ¹ R ² , R ³ , X, Y, Q, Q ′, m and n in the schemes 1 to 3 have the same meanings as described above, and Ha 1 is a halogen. Represents an atom.

a

C

(11-A) (where _n represents 1 <Scheme 1 0

Jl

R CH = CH ₂

mo

, C-NHCH ₂ CH ₂ CR ³

R

g

(1-A) (where n represents 2 <

Scheme 2

, N¾— ·

Imagination

(1-B)

Scheme 3

(1) Scheme 1 synthesizes intermediate c by reacting benzylamine derivative a with α-nitrogenoketon derivative b, and synthesizes intermediate c. The reactive compound d of the acetic acid derivative is reacted to form an N-benzylamide derivative _e, and finally, the N-benzylamide derivative e is closed. Represents a method for producing the compound (111A) of the present invention.

① First-step reaction Usually, b O .5 or more with respect to a; L 0 equivalent, preferably 0.8 to.

Use 5 equivalents

The reaction proceeds without solvent, but is usually accelerated by the use of a solvent. Hexane, heptane, rig mouth as solvent — —

Aliphatic hydrocarbons such as petroleum ether, aromatic hydrocarbons such as benzene, toluene, xylene, black benzene, black mouth Halogenated hydrocarbons such as salified methylene, ethers such as ethyl ether, dioxan, tetrahydrofuran, etc .; Ketones such as seton, methyl etholetone, etc .; nitriles such as acetonitrile, isopyronitrile, pyridin; N, N — tertiary amines such as ethyl aniline, N, N — dimethyl acetate amide, NN — dimethyl honole amide, N — Acid amides such as methylenpyrrolidone, sulfur-containing compounds such as dimethyl sulfoxide and sulfolane, and mixtures thereof Preferably, the aliphatic hydrocarbons, aromatic hydrocarbons, ethers, ketones, nitriles, acid amides, and the above-mentioned aliphatic hydrocarbons are preferably used. The yellowing compounds and their mixtures are extruded.

Usually, 0.5 to 10 equivalents, preferably 0.8 to 3.0 equivalents, of the base relative to a are used. As bases, pyridin, triethylamine, N, N—dimethylaminolin, N, N—diethylorelin, 4-(N, N — Dimethylamino) pyridine, 1, 4 — Nitrogen-containing organic bases such as diazabicyclo [2.2.2] octane, hydrogenated sodium Inorganic bases such as um, potassium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc. are exposed. Preferably, a trinitroquinamine NN is a nitrogen-containing organic base such as dimethylanilin.

The reaction temperature is usually from 0 to 200 ° C, preferably from room temperature to the reflux temperature of the reaction mixture.

Reaction time is usually from 10 minutes to 96 hours, preferably from 30 minutes to 24 hours

After completion of the reaction, c can be isolated by extraction with an organic solvent.o

② Second stage reaction

From 0.5 to 3.0 equivalents, preferably from 0,8 to 20 equivalents, are used for c.

Examples of the reactive compound d of the acetic acid derivative include an acid anhydride, an acid chloride, an acid bromide, an active ester, and the like.

The reaction proceeds without solvent, but is usually accelerated by the use of a solvent. Hexane, heptane, rig mouth In aliphatic hydrocarbons such as petroleum ether, benzene, toluene, xylene, black mouth as solvents Aromatic hydrocarbons such as benzene, halogenated hydrocarbons such as chloroporous chloromethane, methylene chloride, etc., ethyl ether, dioxane, Ethers such as trahydrofuran, etc., ketones such as aceton, methionole etholetone, etc., acetonitrile and isopuchi. N-trinoles such as _-lonitrinole, pyridine, N, N — tertiary amines such as dimethylanilin, N, N — dimethyl Acid amides such as acetate amide, NN—dimethylaminoformamide, N—methylpyrrolidone, dimethylsulfoxide, Sulfur-containing compounds such as phorolane, water and mixtures thereof are preferred, and the above-mentioned aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons are preferred. , Ethers, ketones, nitriles, acid amides, sulfur-containing compounds and mixtures thereof.

It may be better to use a base for the reaction. In that case, 0.5 to 10 equivalents, preferably 0.8 to 3.0 equivalents, of the base is used. Pyridines, triethynoleamines, N, N—dimethylalanines, N, N—diethylenoline, 4— (N, N—Dimethylaminoamino) N-containing organic bases such as pyridin and 1,4-diazabicyclo [22.2] octane, sodium hydrogenated And inorganic bases such as hydrogenated potassium, sodium hydroxide, potassium hydroxide, sodium carbonate, carbonated carbonate and the like are exfoliated and are preferable. Examples include inorganic bases such as sodium carbonate and potassium carbonate, and nitrogen-containing organic bases such as triethylamine, pyridin and the like.

The reaction is usually carried out at a temperature of from 130 to 150 ° C, preferably from -10 ° C to the reflux temperature of the reaction mixture. _ _

The reaction time usually ranges from 10 minutes to 48 hours, preferably from 30 minutes to 24 hours.

After the reaction is completed, e can be isolated by extraction with an organic solvent.

e is usually closed in the presence of a base.

The reaction usually requires a solvent, and the solvent may be aliphatic hydrocarbons such as hexane, heptane ligne, petroleum ether, benzene and toluene. Aromatic hydrocarbons such as benzene, xylene, and chlorobenzene, halogenated hydrocarbons such as chlorobenzene and methylene chloride, and methyl ether Ethers such as tel, dioxan, tetrahydrofuran, etc., ketones such as acetone, methylethylenoketone, etc., and acetate Nitrites such as nitrinoles and isoptinitronitrile; tertiary amines such as pyridin; N, N-diethylanilinine; N , N — Dimethyl acetate amide, N, N — Dimethyl honolem amide, N — Acid amides such as methylpyrrolidone, dimethylSulfur-containing compounds such as snorex oxide and sulfolane, and phenolic compounds such as methanol, ethanol, propanol, and butyl phenol , Water and mixtures thereof are removed, preferably the above-mentioned acid amides, alcohols and mixtures thereof.

Usually, 0.05 to 5.0 equivalents of base relative to e, preferably — —

Use 0.05 to 3.0 equivalents. As bases, pyridin, triethylenamine, N, N—dimethylaminolinine, N, N—dimethylalanine, 41 (N, N — Nitrogen-containing organic bases, such as dimethylaminoamino) pyridin and 1,4-diazabicyclo [2.2.2] octane, hydrogenated sodium Inorganic bases such as hydrogen hydride, sodium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, etc. , Sodium ethoxide, metal alkoxides, such as potassium tert-butoxide, sodium methyl ester, sodium methyl ester Metal alkyl alcohols, such as trimethyl alcohol, etc., are preferably used. Preferably, sodium hydroxide, hydroxide are used. , Carbonate Na Application Benefits © beam, an inorganic base such as carbonate force Li © beam, na Application Benefits © transom preparative key sheet metal A Le co la such as de one preparative Ruika Oh up al is Ru.

The reaction temperature is usually from 0 to 200 ° C., preferably from room temperature to the reflux temperature of the reaction mixture.

The reaction time usually takes 2 minutes to 24 hours, preferably 5 minutes and 12 hours.

In some cases, the reaction proceeds in the second stage reaction to the third stage ring closure reaction.

(2) Scheme 2 synthesizes an intermediate g by reacting a benzoinoleamine derivative a with a vinylketone derivative ί, and adding the vinegar to the obtained intermediate g. — —

The reactive compound d of the acid derivative is reacted to obtain an N-benzylamide derivative h, and finally the N-benzylamide derivative h is closed. This shows the method for producing the compound of the present invention (11-A). ① First stage reaction

Usually, f 0 .5 to: L 0 equivalent, preferably 0.8 to 3 equivalent is used for a.

The reaction proceeds without solvent, but it is possible to use a solvent. Aliphatic hydrocarbons such as hexane, heptane, rig mouth, petroleum ether, benzene, toluene, xylene, and chlorene as solvents. Aromatic hydrocarbons such as benzene and benzene, halogenated hydrocarbons such as chloromethane and methylene chloride, dimethyl ether, and dioxa Ketones such as acetates, methyl ketones, etc., acetates, etc. Nitrites such as petitlonitrile, N, N — dimethyl acetate amide, N, N — dimethylformamide, N — methyl Acid amides such as pyrrolidone, sulfur-containing compounds such as dimethyl sulfolide and sulfolane, water, and mixtures thereof.Et al Re that.

The reaction temperature is usually from 130 to 150 ° C, and preferably from 110 ° C to the reflux temperature of the reaction mixture.

The reaction time is usually between 10 minutes and 96 hours, preferably 30 minutes. _ _

It takes 72 hours.

G can be isolated by distilling off low-boiling compounds after the reaction is completed.o

② Second stage reaction

The amidation reaction can be carried out under the same reaction conditions as in the second stage of Scheme 1.

③ Third stage reaction

The ring closure reaction can be performed under the same reaction conditions as in the third step of Scheme 1. In the second stage reaction, as in the case of scheme 1, the reaction may proceed to the third stage ring closure reaction.

(3) Scheme 3 represents a method for producing the compound (11-B) of the present invention by reducing the cyclic (thio) amide compound i.

Aluminum hydride, aluminum hydride, sodium borohydride, boron hydride, lithium hydride Metal, hydrogen borohydride, metal hydride complex compounds such as boron hydride tetramethylammonium, boron, aluminum, ketone Metal hydrides such as hydrides such as silicon and tin, metals such as sodium, lithium, magnesium, etc., and catalytic hydrogenation It is.

The reducing agent is usually present in an amount of 0.5 to L; equivalent to i, preferably _ _

Use 0.8 to 10 equivalents.

The reaction usually uses a solvent, and the solvent may be aliphatic hydrocarbons such as hexane, heptane, rig mouth, petroleum ether, benzene, toluene, etc. Aromatic hydrocarbons such as benzene, xylene, and chlorobenzene, halogenated hydrocarbons such as chlorobenzene and methylene chloride, and dimethylene Ethers such as ter, dioxan, tetrahydrofuran, etc., ketones such as aceton, methino ole ethole ketone, etc. Nitrils such as tonitrile and isopyronitrile, liquid ammonia, pyridin, N, N—N-N-N Mines, N, N—Dimethyl acetate amide, N, N—Dimethyl honolem amide, N—Methyl pyrrolidone and other acids Sulfur-containing compounds such as mids, dimethyl alcohol and sulfolane, and alcohols such as methanol, ethanol and propanol , And the power of mixtures thereof, and the above-mentioned aromatic hydrocarbons, ethers, amines, alcohols, and the like And a mixture of these.

The reaction is usually carried out at a temperature of from 150 to 200 ° C., preferably from 150 ° C. to the reflux temperature of the reaction mixture.

The reaction time usually takes 5 minutes to 96 hours, preferably 15 minutes to 48 hours.

If it is necessary to purify the compound of the present invention, recrystallize Separation and purification can be performed by any purification method such as mucous chromatography.

Among the compounds included in the present invention, compounds having an asymmetric carbon include optically active (+) and (1) isomers.

Hereinafter, synthesis examples of the compound of the present invention will be specifically described as reference examples and examples, but the present invention is not limited thereto.o

[Example ]

[Reference Example 1] (3—Cross mouth a a Dimethyl benzoylamino) 2 Synthesis of propanone

3 — Chlorine _α , _α — Dimethyl pentopenolamine 2 g, black mouth — 1.82 g of acetate, 1.39 g of triethylenamine and N, N — A mixture of 20 ml of dimethyl acetate in a nitrogen atmosphere The mixture was stirred at 80 ° C for 3 hours. After allowing the reaction solution to cool, it was poured into 500 ml of water, and extracted with ethyl acetate. After washing with water, the extract is dried over anhydrous sodium sulfate, and the solvent is distilled off under reduced pressure.

8 g obtained as a yellow oil

[Reference Example 2] Synthesis of 4- (3-α α mouth aa dimethyl benzoylamino) 2 —butanone

CH ₃

15.5 g and 3-black mouth, a-dimethyl benzoylamine A mixture of 25 g of dimethyl phenylamine in a nitrogen atmosphere at 60 ° C For 5 hours. After completion of the reaction, the low boiling components are distilled off under reduced pressure. --The objective compound 38. 2 g was thus obtained as an orange oil.

ΓReference example 3 1 N — (3 — chloro α, α — dimethyl benzyl) Ν — (2 — oxopropyl) 3 — thiophene Synthesis of toamide

Reference 1 — (3 — chloro α, α — dimethylbenzylamino) synthesized in Example 1 1 — 2-prono. Non 1.5 g, thiophene 13-acetic acid 0.95 g, 3-(3-dimethylaminopropyl) ethyl carbodiimide Hydrochloride 28 g and dichloromethan

25 ml of the mixture was stirred overnight at room temperature. The solvent is distilled off under reduced pressure, extracted with ethyl acetate, washed with water, saturated aqueous sodium hydrogen carbonate, aqueous solution, saturated saline, and then with anhydrous sodium sulfate. After drying, the ethyl acetate is distilled off, and 1.71 g of the target compound is made viscous. I got it as a file.

_{^ - NMR (CDC 1 3)} , δ (ppm):.... 1 6 5 (6 Η s), 2 2 0 (3 Η, s), 3 3 3 (2 Η, s), 4 3

8 (2 layers, s), 6.67 to 7.5 4 (7 layers, m).

[Reference Example 4] Ν-(3-chloro α. Α-dimethylpenyl) Ν-(2-oxopropyl) 3-pyridinacet Synthesis of amide

Reference Example 1 1 (3—chloro α, α—dimethylbenzylamino) 1-2—prono, synthesized in Example 1. Non-0.77 g, 3-pyridyl acetic acid 0-47 g, 3-(3-dimethylaminoamine)-ethynolecarpodiimide salt 0.66 g of acid salt and dichloromethan A 13 ml mixture was stirred overnight at room temperature. The solvent was distilled off under reduced pressure, a saturated aqueous sodium hydrogen carbonate solution was added, and the mixture was extracted with ethyl acetate. After washing with saturated saline and drying over anhydrous sodium sulfate, ethyl acetate was distilled off to obtain 0,82 g of the target compound as a viscous oil. Was.

.... ½ - NMR ( CDC 1 3), δ (ppm): 1 6 7 (6 Η s), 2 2 2 (3 Η, s), 3 3 1 (2 Η, s), 4 4 3 (2 layers, s), 7.03 to 7.70 (4 layers, m), 8.0 2

88.26 (2 m, m), 8.3 4 88.63 (2 ,, m) Reference Example 5 (-(3 — Black mouth α, α — Dimethylpe (3-year old quinobutyl) 2-Synthesis of thiophenacet amide

O — —

4 — Synthesized in Reference Example 2 (3 — Chloroa, a — Dimethyl benzoylamino) 1-2 — Butanone 1.5 g and carbonic acid Twenty-nine ml of 0.9 g of acetic acid solution was cooled to 115 ° C., and 0.7 ml of 2-thiopheneacetyl chloride was added dropwise. The temperature was raised to room temperature, and the mixture was stirred overnight. The solvent was distilled off under reduced pressure, saturated sodium bicarbonate was added, and the mixture was extracted with ethyl acetate. After drying after washing sulfate anhydride Na Application Benefits © beam with brine and the solvent was evaporated under reduced pressure, preparative thin layer click ii Conclusions grayed La off I over (S i 0 _2, eluent CH ₂ C 1 Purification by ₂ ), 0.68 g of the target compound was converted to yellow oil.

... ½ - NMR (CDC 1 3), δ (ppm): 1 6 5 (6 Η s), 2 1 5 (3 Η, s), 2 7 5 (2 Η, t, J = 8 Η ζ ), 3.69 (2, s), 3.89 (2, t, J = 8), 6.74 to 7.45 (7, m).

[Example 1] 1-1 (3-Black mouth a, a-Dimethyl benzyl) 1-4-Methanol 3-(Chofen 1-3-Tin) 1 3 — Synthesis of pyrroline-1 2 -one (compound A — 4)

N synthesized in reference 3 — (3 — black mouth — αa dimethyl benzene) N (2 — oxopropyl) 3 — thiophenacetoami 2.69 g of the compound was dissolved in 22 ml of ethanol, 0.04 g of potassium hydroxide powder was added, and the mixture was heated under reflux for 15 minutes. After completion of the reaction, the solvent was distilled off under reduced pressure, water was added, and the mixture was extracted with ethyl acetate. After washing with water and saturated saline in that order, drying over anhydrous sodium sulfate, and distilling off the solvent under reduced pressure, the preparative thin-layer chromatography (expanded solution, Compound by purifying with a black hole

07 g were obtained as white crystals.

[Example 2] (3-Black mouth α, α-Dimethyl benzyl) 1-4-Methylene 3-(Pyridine 1-3-inole) 13-Pilo Synthesis of Lin 2 -one (Compound Α-9)

N — (3 — chloro α, α — dimethylbenzene) synthesized in Reference Example 4 — (2 — oxopropinole) 3 — pyridinine 0.8 g of the cetamide was dissolved in 10 ml of ethanol, 0.01 g of potassium hydroxide powder was added, and the mixture was heated under reflux for 15 minutes. After the reaction was completed, the solvent was distilled off under reduced pressure, water was added, and the mixture was extracted with ethyl acetate. After washing with a saturated saline solution, drying over anhydrous sodium sulfate and distilling off the solvent under reduced pressure, the preparative thin-layer chromatography (developing solution, chloroform) : Ethyl acetate = 2 ·: 3) to give 0 g of the target compound as white crystals

[Example 3] 1-1 (3-Black mouth a a-Dimethyl benzene) 1-4-Metal 3-(thiophen 2-dino), 2,,

5, 6 — tetrahydropyridine 1 2 — on (Compound A — 11) One synthesis

N— (3—Cross mouth α, α—Dimethyl benzyl) synthesized in Reference Example 5— (3—Oxoptinol) 2—Chofphena 0.68 g of cetamide was dissolved in 15 ml of ethanol, and 0.03 g of lithium hydroxide powder was added, followed by heating under reflux for 1 hour. After completion of the reaction, the solvent was distilled off under reduced pressure, water was added, and the mixture was extracted with ethyl acetate. After washing with saturated brine, drying over anhydrous sodium sulfate and distilling off the solvent under reduced pressure, column chromatography (Si0 „, developing solvent) CHC 1 ₃₎ by Ri eye compounds in and this you 100/0. the 4 1 g was obtained as a white color crystal.

[Embodiment 4] (3-c α πaa dimethyl benzoyl) 1-3-cyano 4-1 -methyl, 2, 5, 6-tetrahydro Synthesis of pyridin —2—one (compound A — 41)

5 g of 4 (3 π-low αα-dimethylmethylbenzoylamino) synthesized in Reference Example 2, 5 g of cyanoacetic acid, 77 g of cyanoacetic acid,

3 — (3 — dimethylaminopropinole) 1 1 — A mixture of 4.5 g of ethylphenol carbodiimide hydrochloride and 5 Oml of dichloromethane Was stirred overnight at room temperature. The solvent was distilled off under reduced pressure, water was added, and the mixture was extracted with ethyl acetate. After washing with a saturated aqueous solution of sodium hydrogen carbonate and drying over anhydrous sodium sulfate, the solvent is distilled off under reduced pressure, and the obtained crude crystals are collected in an isopropyl ether. By washing with, the desired compound 2.46 g was obtained as brownish white crystals.

[Example 5] 3, 4 — trans — 1 — (3 — black mouth. Α — dimethyl benzene) 4 — methyl 1 3 — (chifone 2) one

— Synthesis of 1 2 — Piberidinone (Compound B—5)

(3,4-trans form) 1 — (3 — α-α, α — dimethyl benzene) synthesized in Example 3 4 — Methyl 3 (thiophene 2 Ill) One 1

2,5,6 — Tetrahydropyridin-1 2 — One 17 g was dissolved in 35 ml of ethyl ether and hydrogenated at room temperature. To the mixture, 0.3 g of uranium was added, and the mixture was stirred for 5 hours. After completion of the reaction, water was added, and the mixture was extracted with ethyl acetate. After drying over anhydrous sodium sulfate, the solvent was distilled off, and the resulting residue was purified by preparative liquid chromatography to obtain 0.28 g of silica. This mixture was dissolved in anhydrous tetrahydrofuran (5 ml) and dissolved in a stream of nitrogen (0.04 g, 55% oil). Was added and the mixture was stirred at room temperature for 30 minutes. After completion of the reaction, 1% aqueous hydrochloric acid solution 20 ml --Poured and extracted twice with ethyl acetate. After washing with a saturated saline solution, drying over anhydrous sodium sulfate and distilling off the solvent, the residue obtained is fractionated. Thin-layer chromatographic (developing solution, black hole) Home: ethyl acetate

= 20: By purifying in 1), 0.14 g of the target compound was obtained.

1 defended.

[Example 6] 3, 4 — trans — 1 — (3 — chloro αa dimethyl benzyl) 4 -methyl 3 fluor 2 -piveridinone (compound Synthesis of B-6)

(3,4-trans form)

(3 — chloro α, α — dimethyl benzene) 1-4-1-3-phenyl, 2, 5, 6-tetrahydropyridine

Dissolve 1.0 g of 2-on in 20 ml of ethanol, add 0.1 g of palladium carbon, add hydrogen at normal temperature and normal pressure and add hydrogen. did . After one reaction, the catalyst was separated by filtration and ethanol was distilled off. Purification of the residue by preparative thin-layer chromatography (developing solution, chromatophore: ethyl acetate = 20: 1) gives the target compound 0. 54 g were obtained.

The structural formulas of the compounds of the present invention synthesized according to the above-mentioned skim or the examples are also shown in Tables 1-A and 1-1B, including the compounds synthesized in the above-mentioned Examples. Table 2 shows the physical properties.

(Table A)

One

Compound No. R 'R ² R ³ n Ym Q

A— 1 Me Me M 3 1 C 1 Q 3

A- 2 Me Me Me 4-1 C 1 5 -C 1 -Q 3

A— 3 Me Me Me ¹ 3 -C 15 -C 1 -Q 3

A- 4 Me Me e ¹ 3 -C 1 Q 4

A— 5 Me Me Me 3 1 C) 1 -Me -Q 5

A- 6 Me Me Me 1 3 1 C 1 2 -C 1 -Q4

A- 7 Me Me Me 1 3 1 C 1 Q 5 3

A— 8 Me Me e 1 3 -C】 Q 5 4

A- 9 Me Me Me 1 3 -C 1 Q 4 2

A- 1 0 Me Me Me 2 3— C] Q 4

A— 1 1 Me Me Me 2 3 -C 1 Q 3

A— 1 2 Me Me e 1 3 -CF ₃ Q 4

A- 1 3 Me Me e 13 -F Q 4

A- 1 Me Me Me e 1 H Q 4

A— 15 Me E t Me 1 H Q 4

A- 16 Me Me e 13 1 C 1 Q 6 6

A- 17 Me Me e 3 -C 12 -M e -Q 21

A-18 Me Me Me 2 3 -C 15 -C 1 -Q 3

A- 1 9 Me Me Me e 2 3 -F Q 3

A- 20 Me Me Me 2 3 -F 5--C 1 -Q 3

A- 2 1 Me Me Me Me 2 3 1 C 1 5--B r -Q 3

A- 2 2 Me Me e 2 3 -F 5--B r -Q 3

A- 2 3 e Me e 23-C 15--M e -Q 3 [Continuation of Table 1_A]

Compound No. n 2 n 3 n I m n

A- -2 4 Me Me Me Me e ί 1 Q6 6

A--2 5 Me Me Me Me 24-C 1 Q 3

A- -26 Me M e Me 23-C 1 2--C 1 -Q 66

A--2 7 Me Me Me Me 2 3 — C 1 2--C 1 -Q 4

A--2 8 Me Me Me Me 2 3 C 1 2, 5 — C 12-Q

A- -2 9 Me Me Me Me 2 3 -C 1 2-

A--3 0 Me Me Me Me 2 3 -C 1 2, 5 1 Br 2-Q 4

A— -3 1 Me Me Me 2 3 1 C 1 5--Me-Q l 9

A- -3 2 Me Me Me 2 3 1 C 1 2, 5 -Me 2-Q 4

A- ■ 3 3 Me Me Me 2 3 1 C 1 5--CHO-Q 3

A- 3 4 Me e Me Me 2 3 1 C 1 3 1 -Me -Q 3

A- 35 5 Me Me Me Me 23-C 12-o 1

A- 3 6 Me Me Me Me 2 3 1 C 1 2

a

n

A- 3 7 Me Me Me Me ά ― Shi 1 Q 1 P

A- 3 8 Me Me Me Me 1 — then 1 CN

A- 3 9 Me Me Me Me 23-1 C〇 ₂ Et

A- 40 Me Me Me 2 3 — C 1 C〇 ₂ H

A- 1 Me Me Me 2 3 — C 1 CN

A— 4 2 Me Me Me 2 3 — C 1 C〇 ₂ P h

Λ- 4 3 Me Me Me 2 3. — C 1 C 0 ₂ tB u

Λ— 4 4 Me Me Me 2 3 -one C 1 3 one C 1 one Q 3

A— 4 5 Me Me Me 2 3-— C 1 Q 2 [No. 1—Continued in Table A] Compound No. R ¹ R ² R 3 n Ym Q

A— 4 6 Me Me Me 2 3 1 C 1 Q 4 3

A— 4 7 Me Me E t 2 3 1 C 1 Q 3

A— 4 8 Me Me Me 2 3 -C 1 Q4 1

A- 4 9 Me Me Et 2 3 1 C 1 Q 4

A— 5 0 Me Me E t 1 3 -C 1 Q 3

A- 5 1 Me Me Et i 3 1 C 1 Q 4

A- 5 2 Me Me H 2 3 1 C 1 Q 3

A— 5 3 Me e t -Bu 1 3 1 C 1 Q 4

A- 5 4 Me Me t 1 Bu 1 3 1 C 1 Q 3

A- 5 5 Me Me Pr 2 3 1 C 1 Q 3

A- 5 6 Me Me Pr 2 3 1 C 1 Q 4

A- 5 7 Me Me Et 2 3 -CF ₃ Q 3

A- 5 8 Me e Me 2 3 -CF ₃ Q 3

A- 5 9 Me Me Et 2 4 One M e Q 3

A- 60 Me Me E t 2 H Q 3

A- 6 1 Me E t E t 2 H Q 3

A- 6 2 Me Me E t 2 2 1 C 1 Q 3

A- 6 3 Me MeEt 2 4 1 C 1 Q 3

A- 6 4 Me e E t 2 4-1 B r Q 3

A- 6 5 Me Me E t 2 3 1 F Q 3

A- 6 6 Me Me Et 24 -F Q 3

A- 6 7 Me E t E ΐ 2 4 -C 1 Q 3 [Continuation of Table 1-A]

Compound No. R ¹ R ² R ³ n Ym Q

A-6 8 H Me E t 2 H Q3

(Table 1-1 B)

Compound No. R ¹ R ² R ³ n Ym

B- 1 Me Me H 2 3 -C 1 Q 3

B-2 Me Me Me 2 3 -C 1 Q 3

(cis-trans mixture)

B-3 Me Me E t 3 -C 1 Q3

(cis-trans mixture)

B-4 Me Me E t 3-C 1 Q3

(trans form)

B- 5 Me Me Me 2 3— C I Q3

(trans form)

B— 6 Me Me Me 2 3— C I Ph

(trans form)

B— 7 Me Me Me 1 3— C I P h

(cis body)

B-8 Me Me Me 1 3— C I P h

(trans form)

However, Ql, Q2, Q3, Q4, Q5, Q19, Q21, Q1, Q42, Q43, Q53, Q54 and Q66 Does the following,

Q2

Q42 Q43 Q53

Q54 Q66

Μe is a methyl group, Et is an ethyl group, Pr is a propynolyl group, Bu is a methyl group, Ph is a phenyl group, and t is evening Represents

One

[Table 2] Compound No. Ή-NMR 0 (ppm)

[Solvent] Physical Properties

1.75 (6H, s), 2.18 (3H, s),

A— 1 3.93 (2H, s), 6.87-7.64 (7H, m)

[CDC1 ₃ ] viscous oil

1.76 (6H, s), 2.18 (3H, s),

A- 2 3.97 (211, s), 6.85 (111, d, J = 4Hz) _!

7.11-7.38 (5H, m)

[CDC1 ₃ ] viscous oil

1.72 (6H, s), 2.13 (3H, s),

A- 3 3.91 (2H, s), 6.76 (1H, d, J = 4Hz) _:

7.04-7.32 (5H, m)

[CDCla] viscous oil

1.74 (6 (1, s), 2.13 (311, s),

A— 4 3.91 (2H, s), 7.03-7.47 (6H, m),

7.68 (111, dd, J = 4,2Hz)

[CDC1 ₃ ] viscous oil [Continued in Table 2] Compound No. 'Η— NMR o (ppm)

[Solvent] Physical Properties

1.79 (6H, s), 2.07 (3H, s), 3.55 (3H, s),

A- 5 4.00 (2H, s), 6.1 (2H, brs),

6.60-6.71 (lH, m), 7.08-7.33 (4H, m)

[CDC1 ₃ ] viscous oil

1.81 (6H, s), 2.05 (3H, s),

A— 6 3.99 (2H, s), 6.91 (IH, d, J = 7Hz),

7.18 (IH, d, J = 7Hz), 7.17-7.49 (4H, m)

[CDC1 ₃ ] viscous oil

1.87 (6H, s), 1.92 (3H, s),

A- 7 4.09 (211, s), 7.10-8.00 (11H, m)

[CDC] viscous oil

1.85 (6H, s), 2.22 (3H, s),

A— 8 4.02 (2H, s), .7.15-8.05 (11H, m)

[CDCU] Melting point 157-160 ° C [Continued in Table 2] Compound No. Ή-NMR δ (ppm)

[Solvent] Physical Properties

1.83 (611, s), 2.19 (3H, s), 4.02 (2H, s) _;

A- 9 7.11-7.47 (4H, m), 7.77-8.06 (2H, m),

8. 3-8.70 (2H, m)

[CDC1 ₃ ] Melting point 144-148 ° C

1.71 (611, s), 1.87 (3H, s),

A— 10 2.43 (2H, t, J = 7Hz), 3.49 (2H, t, J = 7Hz),

6.96 (1H, d, J = 5Hz), 7.10-7.33 (6H, m)

CCDC1 ₃ ] Melting point 137-138 ° C

1.71 (6H, s), 1.93 (3H, s),

A— 11 2.41 (2H, t, J = 6Hz), 3.43 (2H, t, J = 6llz):

6.89-7.32 (7H, m)

[CDCI3] melting point 120-121 ° C

1.81 (6 G I, s), 2.20 (3H, s), 4.01 (2H, s),

A -12 7.20-7.80 (711, m)

[CDCI3] viscous oil [Continued in Table 2] Compound No. Ή-NMR δ (ppm)

[Solvent] Physical Properties

1.82 (6H, s), 2.21 (3H, s), 3.98 (2H, s),

A— 13 6.93-7.78 (7H, m)

[CDC1 ₃ ] Melting point 105-106 ° C

1.84 (6H, s), 2.17 (3H, s), 3.90 (2H, s) _;

A-14 7.20-7.60 (7H, m), 7.80 (1H, d, J = 3Hz)

[CDC1 ₃ ] Melting point 108-109 ° C

0.86 (3H, t, J = 7Hz), 1.73 (3H, s) _:

A—15 2.07 (2H, q, J = 7Hz), 2.14 (3H, s).

3.88 (2H, s), 7.29-7.79 (8H, m)

[CD port ₃ ] viscous oil

1.74 (6H, s), 1.92 (3H, s), 3.97 (2H, s)

A— 16 7.18-7.90 (9H, m)

[CDC] viscous oil

1.79 (6H, s), 2.48 (3H, s), 2.71 (3H, s) _;

A— 17 4.00 (2H, s), 7.22-7.28 (4H, m),

8.04 (1H, s)

'' [CDC] Viscous oil [Continued in Table 2] Compound No. Ή-NMR δ (ppm)

[Solvent] Physical Properties

1.72 (6H, s), 2.00 (3H, s),

2.44 (2H, t, J = 7Hz), 3.45 (2H, t, J = 7Hz) _:

A— 18 6.68 (1H, d, J = 5Hz), 6.80 (1H, d, J = 5Hz),

7.24-7.34 (4H, m)

[CDC1 _3] mp 125-130 ° c

1.74 (6H, s), 1.96 (3H, s),

A— 19 2.43 (2H, t, J = 7Hz), 3.44 (2H, t, J = 7Hz) _;

6.90-7.34 (7H, m)

[CDC1 _3] melting point of 95-97 t

1.72 (6H, s), 1.99 (3H, s),

A— 20 2.43 (2H, t, J = 7Hz), 3.44 (2H, t, Hz) _:

6.60-7.40 (6H, m)

[CDCh] Melting point 125-130 ° C

1.73 (6 g I, s), 2.00 (3H, s),

2.43 (211, t, J = 7Hz), 3.44 (211, t, J = 7Hz) _:

A— 21 δ.65 (111, d, J = 4llz), 6.93 (Hi d, J = 4Hz),

7.27-7.33 (4H, m)

[CDC1 _3] melting point of 127-129 t

[Continued in Table 2] Compound No. Ή-NMR δ (ppm)

[Solvent] Physical Properties

1.66 (9H, s), 2.49 (2H, t, J = 7Hz),

A-26 3.58 (2H, t, J = 7Hz), 7.20-7.75 (8H, m)

[CDC1 ₃ ] viscous oil

1.68 (6H, s), 1.78 (3 to I, s),

2.44 (2H, t, J = 7Hz), 3.50 (211, t, J = 7Hz) _!

A -27 6.77 (IH, d, J = 6Hz), 6.99 (IH, d, J = 6Hz),

7.05-7.31 (4H, m)

[CDCU] Melting point 134-136 t

1.70 (6H, s), 1.82 (3H, s),

A-28 2.45 (2H, t, J = 7Hz), 3.51 (2H, t, J = 7Hz),

6.67 (IH, s), 7.22-7.32 (4H, m)

[CDCh] viscous oil

1.70 (6H, s), 1.78 (3H, s),

A -29 2.44 (211, t, J = 7Hz), 3.53 (2H, t, J = 71lz) _;

6.78 (111, d, J = 6Hz), 7.12-7.32 (511, m)

[CDC1 ₃ ] Melting point 134-137 ° C [Table 2 continued] Compound No. 'Η— NMR δ (ppm)

[Solvent] Physical Properties

1.69 (6H, s), 1.80 (311, s),

A -30 2.44 (2H, t, J = 7Hz), 3.52 (2H, t, J = 7Hz) _:

6.78 (1H, s), 7.20-7.40 (411, m)

[CDC1 _3] mp 149-152 ° C

1.70 (611, s), 1.88 (3H, s),

2.44 (2H, t, J = 7Hz), 2.68 (3H, s),

A— 31 3.51 (2H, t, J-7Hz), 7.06 (1H, s),

7.15-7.41 (4H, m)

[CDCU] viscous oil

1.69 (6H, s), 1.74 (3H, s), 2.10 (3H, s)

2.33 (3H, s), 2.42 (2H, t, J = 7Hz),

A— 32 3.49 (211, t, J = 7llz), 6.38 (1H, s),

7.19-7.31 (4H, m)

[CDCU] viscous oil [Continued in Table 2] Compound No. Ή-NMR δ (ppm)

[Solvent] Physical Properties

1.73 (6H, s), 1.99 (3H, s),

2.49 (2H, t, MHz), 3.49 (2H, t, J = 7Hz) _!

A -33 7.00 (IH, d, J = 4Hz), 7.21-7.31 (4H, m),

7.63 (IH, d, J = 4Hz), 9.89 (1H, s)

[CDC1 _3] melting point of 139-142 t

1.71 rat s), 1.79 (3H, s), 1.97 (3H, s),

A -34 2.45 (2H, t, J = 7Hz), 3.50 (2H, t, J = 7Hz),

6.82 (IH, d, J = 6Hz), 7.13-7.31 (5H, m) points

[CDC1 _3] melting point of 398-102 t:

7

4 2

1.69 (6t l, s), 1.80 (3H, s),

A— 35 2.43 (211, t, J = 7Hz), 3.60 (2H, t, Hz),

6.87 (111, d, J-6llz), 7.05-7.50 (5H, m)

[CDCU]

1.30 (3H, t, J = 7llz), 1.69 (9H, s),

2.45 (2H, brt), 3.57 (211, t, J = 7Hz),

A— 36 4.24 (2H, q, J = 7Hz), 6.86 (111, d, J = 5llz) _;

7.10-7.50 (5H, m)

[CDCI3] viscous oil

[Continued in Table 2] Compound No. Ή-NMR δ (ppm)

[Solvent] Physical Properties

1.72 (6H, s), .2.25 (3H, s),

A— 41 2.50 (2H, t, J = 7Hz), 3.44 (2H, t, J = 7Hz) _;

7.13-7.38 (4H, m)

[CDC1 ₃ ] Melting point 112-114 ° C

1.71 (6H, s), 2.04 (3H, s),

A -42 2.34 (211, t, J = 7Hz), 3.38 (2H, t, J = 7Hz) _;

7.20-7.40 (9H, m)

[CDCI3] Melting point 95-99 ° C

1.44 (9H, s), 1.64 (6H, s),

A -43 1.87 (311, s), 2.21 (2H, t, J = 7Hz),

3.27 (211, t, J = 7Hz), 7.15-7.30 (4H, m)

[CDCI3] viscous oil

1.69 (6H, s), 1.82 (311, s),

A— 44 2.44 (211, t, J = 7Hz), 3.49 (2H, t, J-7Hz),

6.86 (111, d, J = 5Hz), 7.10-7.46 (5H, m)

[CDCI3] Melting point 98-100 ° C

¾ 2

s * i [Continued in Table 2] Compound No. Ή-NMR δ (ppm)

[Solvent] Physical Properties

1.16 (9H, s), 1.75 (6H, s), 4.22 (2H, s),

A— 53 6.90-7.40 (7H, m)

[CDC1 _3] melting point of 134-135 t

1.20 (9H, s), 1.75 (6H, s), 4.28 (2H, s),

A— 54 6.90-7.50 (711, m)

[CDCla] Melting point 126-128 ° C

0.88 (3H, t, J = 6.5Hz), 1.19-2.39 (4H, m):

A— 55 1.72 (6H, s), 2.41 (211, t, J = 6Hz),

3.44 (2H, t, J = 6Hz), 6.74-7.53 (7H, m)

[CDC] viscous oil

0.83 (3H, t, J = 6.5Hz), 1.20-2.25 (4H, m),

A— 56 1.69 (611, s), 2.38 (2H, t, J = 6Hz),

3.42 (2H, t, J = 6Hz), 6.75-7.34 (7H, m)

[CDC1 ₃ ] viscous oil

One. 80Ϊ-Α0Ϊ? $ 1 [ ^Ε ΐ303]

( ^ω 'WD 05 "-06' 9

'Β' d "2-ΟΤ" 2 9 1 V '(s Ή9) EM' (zHOf ΉΕ) Ο 6Z-8Z 1

( ^ω Ή) Ce Ί-ΟΒ "9

ε9—v

'(ζ | Ι5 Γ Ή2) 9' (ζΗΟΓ 'b Ή2) ΐ2

'(s Ή9) 8Γΐ' (zHS f l) O 'ΐ

^ [ ^ε Ι303]

8) On-S8'9 Appendix VH) Ce '8

'(' Η9) ^ '2-00' 2 '(s ΉΕ) ΐ ΐ9-1 V

Ή8) 0ΐ ΐ '(ΖΗΟΓ ΉΕ) 58 "0

90flO / e6df / JDd ZL LS8L0 / P6 O

[Continued in Table 2] Compound No. Ή-NMR δ (ppm)

[Solvent] Physical Properties

1.66 (6H, d, J = 2Hz), 1.79-2.40 (4H, m),

B— 1 3.43 (2H, t, J = 6Hz), 3.68-3.99 (IH, m) _:

6.70-7.74 (7H, m)

[CDC] viscous oil

0.68-1.10 (3H, m), 1.62 (6H, d, J = 3Hz),

B- 2 1.69-2.50 (3H, m), 3.21-3.99 (3H, m),

6.72-7.46 (7H, m)

[CDCU] viscous oil

0.63-1.42 (3H, m), 1.64 (6H, d, J = 2.5Hz) _;

B- 3 1.78-2.33 (5H, m), 3.29-4.11 (3H, m),

6.75-7.42 (7H, m)

[CDC1 ₃ ] viscous oil

0.69-1.35 (5H, m), 1.52 (6H, d, J = 4Hz) _;

B— 4 1.78-2.36 (3H, m), 3.37 (IH, d, J = 4Hz),

3.41-3.64 (2H'm), 6.67-7.30 (7H, m)

[CDCU] viscous oil

Righteousness Examples of the compounds of the present invention synthesized according to the above-mentioned scheme or Example 6 include the above compounds A-1 to A-68 and B-1 to B-18. As shown in Tables 3-1 and 3-2, the present invention is not limited by these.

[Table 3-1]

R R R Ym Q or cr

HHHHC〇 ₂ HHHH 3-C 1 C0 ₂ HHHH 3 -C 1 Q 3 HHH 3-1 C 1 Q 4 HH Me HC〇 ₂ HHH Me 3-C 1 C〇 ₂ HHH Me 3-1 C 1 Q2 HH Me 3-1 C 1 Q 3 HH Me 3 1 C 1 Q 4 HHE t HC〇 ₂ H

H H E t 3-C 1 Q 3

HHP r 3 -C 1 C〇 ₂ H

H H P r 3-C 1 Q 3

HH i-i P r HC〇 ₂ H

H H i—P r 3 1 C 1 Q 3

H Me HHC〇 ₂ H

H M e H 3 1 C 1 Q 4

H Me Me H C0 ₂ H

H Me Me 3 -C 1 Q 2

H Me Me 3-C 1 Q 3

H Me Me 3-C 1 Q 1

H Me E t HC〇 ₂ H [Continued from Table 3-1]

R ¹ R ² R ³ Ym Q or Q '

HM e E t 3 C 1 C〇 ₂ E t

H M e E t 3, 5 —C I 2 Q 3

H E t Me 3 1 C 1 CN

H E t Me 3 -C 1 Q 3

H i-ichi Pr Me HC〇 ₂ H

Me Me HHC〇 ₂ H

Me Me H 3 -F Q 3

Me Me H 3 -C 1 C0 ₂ H

Me Me H 3 1 C 1 Q3

Me Me H 3 1 C 1 1 Q4

1

Me E t HHC u〇 ₂ H

Me Me Me HC_〇 ₂ a 1 H

1

Me Me Me H 3 -M e -Q 1

Me Me Me Me H Q 2

Me Me Me H 4 OM e -Q 2

Me M e Me H Q3

Me Me Me H 3 -C 1 -Q3

Me Me Me H Q4

Me Me Me H

Me M e Me H

Me Me Me H 4 -OM e -Q 4

Me Me Me H 5 [Continued from Table 3-1]

R ¹ R ² R ³ Ym Q or Q '

M e M e M e H 2— M e -Q 2 1

M ee Me e H 5 -CF ₃ -Q37

a

Me Me Me 3 1 C 1 C〇 ₂ P h

Me Me Me 3 1 C 1 Q 1

Me Me Me 3 -C 1

Me Me Me 3 1 C 1 Q2

M e Me M e 3 1 C 1 2 -C 1 -Q 2

Me Me Me 3 1 C 1 4 -C 1 -Q2 [Table 3-1 continued]

R ¹ R ² R ³ Ym cr or Q '

Me Me Me 3 -C 1 4 -OMe-Q2

Me Me Me 3 C 1 4 -M e -Q 2

Me Me Me 3 One C 1 Q 3

Me Me Me 3 1 C 1 3-C 1 -Q3

Me Me Me 3 1 C 1 3 -Me-Q3

Me Me Me 3 — C 1

Me Me Me 3 1 C 1 5 -C 1 -Q 3

Me Me Me 3 1 C 1 5— B r— Q 3

Me Me Me 3 — C 15 -Me-Q3

〇

>

[Continued from Table 3-1]

R ¹ R ² R ³ Ym Q or cr

Me Me Me 3-1 C 1 1-1 Me— Q 6

Me Me Me 3 1 C 1 Q7

Me Me Me 3 1 C 1 4 -C 1 -Q 7

Me Me Me 3 -C 1 Q8

Me Me Me 3 1 C 1 3 -CF ₃ -Q8

Me Me Me 3 — C 1 3 -Me-Q8

Me Me Me 3 1 C 1 5 -C 1 -Q8

Me Me Me 3 1 C 1 Q 9

Me Me Me 3 1 C 1 4 -C 1 -Q9

Me Me Me 3 -C 1 Ql 0

Me Me Me 3-1 C 1 4 1 -Me -Q10

Me Me Me 3 — C 1 4 1 C 1 -Q10

1

Me Me Me 3 1 C 1 Q 1 1 G!

Me Me Me 3 — C 1 3 1 Me e-Qll

Me Me Me 3-1 C 1 5 -Me -Qll

Me Me Me 3 1 C 1 Q 1 2

'Me Me Me 3 — C 1 4 -Me -Q12

Me Me Me 3 — C 1

Me Me Me 3 — C 1 l-Me-4-Cl-Q13

Me Me Me 3 -C 1 He-5- CI- Q 14

Me Me Me 3. — C 1 l-Me-3, 5-Cl ₂ -Q14

Me Me Me 3 · — C 1 1 -Me -Q15 [Continued from Table 3-1]

R ¹ R ² R ³ Ym Q or Q '

M e Me Me e 3— C 1 l- e-4-Cl-Q15

M e M e e 3— C 1 Q l 6

Me Me Me 3 1 C 1 4 -Me-Q16

Me Me Me 3 1 C 1

Me Me Me 3 1 C 1 Q 1 7

Me Me Me 3-1 C 1 2 -Me-Q17

Me Me Me 3 1 C 1 2-Cl-5-Me-Q17

Me Me Me 3 1 C 1 Q 1 8

Me Me Me 3 -C 1

Me Me Me 3 1 C 1 2, 4-Me ₂ -Q18

1

Me Me Me 3 1 C 1 1 1 Q l 9

Me Me 'Me 3 1 C 1

1 a

Me Me Me 3 -C 1 Q2 0 D I

Me Me Me 3 1 C 1 2 -Me -Q20

Me Me e 3 1 C 1 2, 5-e ₂ -Q20

Me Me Me 3 1 C 1 2, 5-Cl ₂ -Q20

Me Me. Me 3 1 C 1 Q2 1

Me Me Me 3 1 C 1

Me Me Me 3— C 1 4 -Me-Q21

Me Me Me 3 1 C 1

Me Me e 3 -C 1 1 -Me -Q23

Me Me Me 3 1 C 1 1 -Me -Q24 [Table 3-1 continued] n 1 P 2 1 3

JA I JJ1

Me Me Me Me Shishi i 丄, 4 ichi Me_w ¾

Μ e λ M Λ c e M eo—— し丄 1, -Me ₂ -Q24

Μ e M e M e d— 1 Q 2 5

Μ e Me Me Me — then 1 Q 2 6

Μ e Me Me Me ά 1 Q 2 7

,

Μ e Me Me 3-C 1 Q 2 8

1

Me Me Me 3-C 15 -CH ₃ -Q37

Me Me Me 3— C 1

Ym [Continued from Table 3-1]

R 'R ² R ³ Ym Q or Q'

M e Me e 3 -C 1 3 — C 1 -Q45 e Me e 3 3 C 1 Q 4 6

Me Me Me Me 3 1 C 1 Q 7

Me Me Me Me 3 1 C 1 4

Me Me Me 3 1 C 1 Q 4 8

Me Me Me Me 3-C IQ 9

M e M e M e 3 -C 1 3 1 C 1 -Q49

Me Me Me 3 1 C 1 Q 5 0 e Me Me 3 1 C 1 Q 5 1

M e Me Me 3 e C) n ^ = 1 0 c 6 Q

Me Me Me Me 3 1 C] 1 Q 5 3

Me MeMe 3 C 1 Q 5 4

1

Me Me Me 3 3 C 1 Q 5 5 a

Me Me Me 3— C 1 Q 5 6

M e Me Me 3 -C 1 Q 5 7

Me Me Me 3 3 C 1 Q 5 8

Me 3 Me C 1 Q 5 9

M e Me Me 3— C 1 Q 6 0

M e Me Me 3 1 C 1 Q 6 1

Me Me Me 3 3 C 1 Q 6 2 e Me Me 3 1 C 1 Q 6 3

M e Me e Me 3 -C 1 Q 6 4 [Continued from Table 3-1]

R ² R ³ Ym Ci or Q 'e Me Me 3 C 1 Q 6 5

Me Me Me 3 1 C 1 Q6 6

[Continued from Table 3-1]

R ¹ R ² R ³ Ym Q or Q '

Me Me Me 3 -C 11 1 Me -Q86

Me Me Me 3 1 C 1

Me Me e 3 1 C 1 1 1 Me— Q87

Me Me Me 3 -C 1 Q8 8

Me Me Me 3 -C 1 Q8 9

Me Me Me 3 -C 1 Q 9 0

Me Me Me 3 1 C 1 Q 9 1

Me Me Me 3 1 C 1 Q9 2

Me Me Me 3-C 1 Q9 3

Me Me Me 3— C 1 Q9 4

Me Me Me 3 -C 1 Q9 5

Me 3 1 C 1 n 1

Me Me q R

Me Me Me 3 1 C 1 Q9 7

M e 3-C 1 Q 9 8 J-

Me Me

Me Me Me 3 1 C 1 Q9 9

M e Me M e 3 1 C 1 Q l 0 0

Me Me Me 3 1 C 1 Q 1 0 1

Me Me Me 3-1 C) Q 1 0 2

Me e Me 3-C 1 Q 1 0 3

Me Me Me 3 -C 1 Q 1 0 4

Me Me Me 3 -C 1 Q 1 0 5

Me Me Me 3 -C 1 Q 1 0 6 [Continued from Table 3-1]

R ¹ R ² R ³ Ym Q or l '

Me Me Me 3 1 C 1 Q 1 0 7

Me Me e 3— C 1 Q 1 0 8

Me Me Me 3 -C 1 Q 1 0 9

Me Me Me 3 1 C 1 Q 1 1 0

Me Me Me 3 1 C 1 Q 1 1 1

Me Me Me e 3 -C 1 Q 1 1 2

Me Me Me 3 1 C 1 Q 1 1 3

Me Me Me 3 1 C 1 Q 1 1 4

Me Me Me 3 1 C 1 Q 1 1 5

Me Me Me 3— C 1 Q 1 1 6

Me Me Me 3 1 C 1 Ql 1 7

Me Me Me 3 1 C 1 Q 1 1 8

Me Me Me 4-1 C 1 CN

Me Me Me 4 -C] C0 ₂ H

Me Me Me 4-1 C 1 Q 1

Me Mee 4 -C 1 Q 2

Me Me Me 4 1 C 1 Q 3

Me Me Me 4-1 C 1 3 -C 1 -Q3

Me Me Me 4-1 C] 5 -C 1 -Q 3

Me Me Me 4-1 C 1 Q4

Me Me Me 4 -C 1 2 -C 1 -Q4

M e Me Me e 4 1 C 1 4 -C 1 -Q 4 [Continued from Table 3-1] n 1

R R R Ym Q or Q '

M e e e 4— C 1 1-Me- 5--Q 14

Me Me Me Me 3, 5, 5-C 1 2 Q 1

Me Me Me Me 3, 5, 5-C 1 ₂ Q2

Me Me Me 3, 5-C 1 2 Q 3

Me Me Me 3, 5-C 1 2 Q 4

Me Me Me 3, 5-C 12 2— C 1 one Q 4

Me Me M e 3, 5-C 12 i— fie— 3—shi i— 丄 4

Me Me e 3, 5-C 1 ₂ l-Me-3, 5-C12-Q14

Me Me Me Me 3, 5, 5-C 1 2 Q 1

M e M e M e 3, 5-C 1 ₂ 3 1 C 1 -Q41

Me Me Me Me ₃ -CF ₃ Q 3

Me Me Me 3 -CF ₃ Q 4

Me Me Me 3-e Q 3

Me Me Me 3 One Me Q 4

Me Me Me 4 One Me Q 3

Me Me Me 4 I Me Q4

Me Me Me 3 -O e Q 3 [Continued from Table 3-1]

R ¹ R ² R ³ Ym Q or Q

MeMeMe3—OeQ4eMe—UMe e.

,

Me Me Me Me 4—OM e Q 4

Me M e E t 3—C] Q 3

Me M e E t 3 1 C 1 Q 4

M e M e Pr 3 -C 1 C〇 _{2 He} M e Pr 3 — C 1 Q 3

Me MePr 3 1 C 1 Q 4

Me Me i -P r 3 1 C 1 1 C〇 ₂ H

〇

Me Me i -P r 3 1 C 1 Q 3

Me Me i 1 Pr 3 1 C 1 Q 4 1

Me E t Me HC〇 ₂ H

Me E t Me H Q 3

Me E t Me H Q 4

Me E t Me 3 -C 1 C〇 ₂ H

Me E t Me 3 -C 1 Q 1

Me E t M e 3 1 C 1 3 -M e -Q 1

M e E t Me 3 -C 1 Q2

Me E t Me 3 1 C 1

Me E t Me 3 1 C 1 Q3

Me E t Me 3 -C 1 3 -C 1 -Q 3 [Continued from Table 3-1]

RR ² R Ym Q or Q

M e E t M e 3—Shi 1

Μ e E t M e — one 1 one 1 — U 4

Μ e-E t M e d—shi 1 4—shi 1 — 4

Μ e E t M e 1 1 l-Me-5-Cl-Q14

Μ e E t M e 3— C 1 l-Me-3, 5 -shi "-Ql4

Μ e E t M e 3 1 C 1 Q l 9 e E t M e 3 1 C 1 Q 4 l

Me E t Me 3 1 C 1 Q 3

Me E t Me 4 1 C 1 Q 3

Me E t Me 4— C 1 3 -C l -Q 3

Me E t Me 4 1 C 1 I Q4

Me E t Me 4-1 C 1 2-C l-1 Q 4

Me E t Me 4-1 C 1 P

M e M e t -Bu 3 -C 1 Q 3

M e M e t -B u 3 1 C 1 Q 4

M e M e E t HC〇 ₂ H,

'e Me E t H Q 3

Me Me E t H Q 4

M e Me E ΐ C〇 ₂ H

Me Me E t 3 -CF ₃ Q 3

Me Me E t 3 1 CF ₃ Q 4

Me Me E t 3 -FC〇 ₂ I-I [Continued from Table 3-1]

R ¹ R ² R ³ Ym Q or Q '

Me Me E t 3 -F Q 3

Me Me E t 3 -F Q 4

Me Me Et 4 Me C〇 ₂ H

Me Me E t 4 Me Q 3

Me Me E t 4 -M e Q4

Me Me E t 2 One C 1 C〇 ₂ H

Me Me E t 2 One C 1 Q 3

1

Me Me E t 2 -C 1 Q 4

Me Me E t 4 1 C 1 C〇 ₂ H

Me Me E t 4 One C 1 Q 3

Me Me E t 4 1 C 1 Q 4

Me Me E t C0 ₂ H

Me Me E t 4-1 Br Q 3

M e Me e E ΐ 4 -B r Q 4

Me Me Et 4 1 FC〇 ₂ H

Me Me E t 4 One F Q 3

Me Me E t 4 -F Q 4

HM e E t HC〇 ₂ H

H e E t H Q 3

H M e E t H Q 4

Me E t E t H C0 ₂ H

Me E t E t HQ 3 --

[Continued from Table 3-1]

R R R Ym Q or Q '

M e E t E t HQ 4 Me E t E t 3-1 C 1 C0 ₂ H Me E ΐ E t 3-1 C 1 Q 3 Me E t Et 3-1 C 1 Q4 Me E t Et 4-1 C〇 ₂ H Me E t E t 4 1 C 1 Q 3 Me E t E t 4 1 C 1 Q4 Me Me HHQ 3 Me Me HHQ 4

[Table 3-2]

Or

Two

1 Iv R ³ ymn,

x ri M e ri P h i ΓΊ lL ri P h n n q

M β o i

1Ph

H hi I 0 — then 1 P

H M e n

H H t H 2 -F-P h

Γ)

H H M e 3—Shi 1 2 -F-P h

H H 3—I 2 -F-P h

H H M e -C 1 -P h

H H doodle t 2 -C 1 -P h

H H M e 3— C 1 2 -C 1 -P h

I- 1 Me Me 3 -C 1 2 -FP h [Continued from Table 3-2]

R ¹ R ² R ³ Ym Q '

H Me E t 3 1 C 1 2 -F-P h

H Me Me H 2 -C 1 -P h

H Me E t H 2 -C I-P h

H Me Me 3— C 1 2 -C 1 -P h

H Me E t 3-C 1 -C 1 -P h

H Me Me H 2 -Me -P h

H Me, E t H 2 -M e-P h

H Me Me 3 1 C 1 2— Me— P h

H Me E t 3-C 12 -Me -P h

Me Me H H P h

Me Me Me H P h

M e Me E t H P h

Me Me H 3 1 C 1 P h

Me Me Me 3-1 C 1 P h

Me Me E t 3-C 1 P h

Me Me H H 2 -F-P h

Me e Me H 2 -F-P h

Me Me E t H 2 -F-P h

Me Me H 3 1 C 1 2 -F-P h

Me Me Me 3 1 C 1 2 -F-P h

Me Me E t 3 1 C 1 2 -F-P h

Me Me HH 2 -C 1 -P h [Continued from Table 3-2]

R ¹ RR Ym Q

Μ e M e M e -C 1 -P h

Μ e M e L t H 2 -C 1 -P h

Μ e M e H 3— C 1 2 -C 1 -P h

Μ e M e M e 3 1 C 1 2 -C 1 -P h

Μ e M e E t 3 1 C 1 2 -C 1 -P h

Me Me H H

Μ e M e M e H 2 1 M e— P h

Μ e e E t H B—M e— r n

Μ e M e H 3— C 1 2— Me— P h

Μ e Me Me Me 3 1 C 1 2 -Me -P h

1

Me Me E t 3 1 C 1 2— Me— P h

Me E t H. H P h 1

. Me E t M e H P h

M e E t E t H P h

Me E t H 3-1 C 1 P h

M e E t M e 3— C 1 P h

Me E t E t 3— C 1 P h

Me E t H H 2 -F-P h

Me E t Me H 2 -F-P h

Me E ΐ E t H 2 -F-P h e E t H 3-C l '2 -F-P h

Me E t Me 3 -C 1 2 -FP h one

[Continued from Table 3-2]

R R Y m Q

M e L t dani t d—shi 1—one P h

M e L t ri one 1 — r n λ Μ Λe e t M e n L——i i —— Π

Μ e L · ∑ 2— C 1 one P

Μ e T?

£ I ri 0―Sh 1 2― C 1Ph

Μ e dani t M e d—Shi 1 2 -C 1 -P

Μ e dani t ∑ t 0 `` 1 -C 1 -P h

Μ e dani t H hi

Μ e E t M e Π

Μ e E t dani t M 2 -Me -P h

Me E t H 3 1 C 1

1

Me E t Me 3 1 C 1 2-1M e -P h

Me E t E t 3-1 C 1 2-1 Me-1 P h

Me Me HH 2 -CF ₃ -P hrz

Me Me H H 3 -C F3 one P h

However, in Tables 3-1 and 3-2, Me is a methyl group, Et is an ethyl group, Pr is a propynol group, Bu is a butyl group, Ph represents a phenyl group, i represents an iso, t represents evening, and Q 1 to Q 11

8 represents the following: // £ 6dfD.S80 / 6 OIiM

σ

o

95

Q19 Q20 Q21

Q55 Q56 Q57

Ό

Q58 Q59 Q60

Q68

, Ν, _Ν八, ノ² ,

Q70 071 072

Q89 Q90 , Ν, to Ν, Ν,

Q91 Q92 Q93

,

'Ν'

Q100 Q101 Q102

Q106 Q107 Q108

Q112 Q113 Q114

Q115 Q116 Q117

N—— N- or

, 6

Q118 In applying the compound of the present invention as a herbicide, generally, a suitable carrier, for example, Cray, tanolek, bentonite, silica, etc. Solid carriers such as algae soil white carbon, or water, alcohols (isoprono, phenol, butanol, pentanoreal) Calls, phenolic furyl alcohol, etc.), aromatic carbohydrates (toluene, xylene, etc.), ethers (anisoles) ), Ketones (cyclohexanone, isophorone), esters (butyric acid ester, etc.), acid ― ―

Can be used in combination with liquid carriers such as benzenes (eg, methylpyrrolidone) or halogenated hydrocarbons (eg, chlorbenzen). If desired, surfactants, emulsifiers, dispersants, penetrants, spreading agents, thickeners, antifreezing agents, anti-caking agents, stabilizers, disintegrators, etc. It can be put into practical use in any form such as wettable powder, dry flowable, flowable, powder, granule, gel and the like.

If necessary, the compound of the present invention may be mixed with other kinds of herbicides, various insecticides, fungicides, plant growth regulators, synergists and the like at the time of preparation or spraying.

In particular, the combined use with other herbicides reduces the cost by reducing the amount of applied herbicide, and reduces the herbicidal spectrum due to the synergistic effect of the mixed herbicide. It can be expected to expand and have higher herbicidal effects. At this time, it is possible to combine with several known herbicides at the same time. The types of herbicides to be used in combination with the compound of the present invention include, for example, farm chemicals and hoods (Farm Chemicals H andook). There are compounds listed in the 1991 edition.

The amount of the compound of the present invention applied as a herbicide may vary depending on the application scene, time of application, application method, cultivated crops, etc., but generally, the effective component amount is hectare ( ha) 0.0000 per 〜: L 0 kg Approximately, preferably about 0.001 to 5 kg.

Next, specific examples of the formulation of the preparation when the compound of the present invention is used are shown. However, the formulation examples of the present invention are not limited to these. In the following formulation examples, "parts" means parts by weight.

(Wettable powder)

5 to 80 parts of the compound of the present invention

Solid support 0 to 85 parts

Surfactant 1 to 10 parts

Others 0 to 5 copies

Other examples include anti-caking agents and the like.

(Milk)

Compound of the present invention 30 parts

Liquid carrier 30 to 95 parts

Surfactant 5 parts

Other 0

Other examples include stabilizers and the like.

(Flour-free agent)

5 to 70 parts of the compound of the present invention

Liquid carrier 5 to 6 5 parts

Surfactant 0.1 to 12 parts Other 0.30 parts, for example, deicing agents, thickeners, etc.

[Granular wettable powder (dry flowable)]

Compound of the present invention 20 to 90 parts Solid carrier 9 to 60 parts Surfactant 1 to 20 parts Other 0 to 40 parts Others include, for example, disintegrants and the like. .

(Granules)

0.010 parts of the compound of the present invention 90 to 999.9 parts of solid carrier and 0 to 5 parts of other

[Formulation Example 1] wettable powder

Compound A of the present invention-1 150 parts

J C Light P P P 4 3

(Kaolin-based cranes: J-Kright Industry Co., Ltd.)

(Anionic surfactant: Toho Chemical Industry Co., Ltd., PP name) Lunox 100 C 3 parts

(Anionic surfactant: Trade name of Toho Chemical Industry Co., Ltd.) Force plex # 80 (anti-caking agent) 2 parts

(White carbon: brand name of Shionogi & Co., Ltd.)

The above is uniformly mixed and ground to form a wettable powder.

[Formulation Example 2] Milk

Compound A of the present invention — 43 parts

Xylene 7 6 parts

Isso Holon 5 copies

Sonole pole 3 0 5 X 6

(Mixture of nonionic surfactant and anionic surfactant, trade name of Toho Chemical Industry Co., Ltd.)

The above are mixed uniformly to form an emulsion

[Formulation Example 3] Flour

Compound A 3335 parts of the present invention

Agrisol S — 7 1 1 8 copies

(Non-ionic surfactant: Kao Corporation)

Lunox 100 0 0 C 0.5 part

(Anionic surfactant: Trade name of Toho Chemical Industry Co., Ltd.)

1% Mouth Drain water 20 parts

(Thickener: Loan-Poulenc brand name)

Ethylene glycol (antifreeze) 8 parts Mix 28.5 parts or more of water evenly to obtain a flowable agent

[Formulation Example 4] Granular wettable powder (dry flowable)

Compound A of the present invention — 1077.5 parts

No.10

(Anionic surfactant: Kuraray Soprene Chemical Co., Ltd.

Knox 2 Rex Ν 5 copies

(Anionic surfactant: brand name of Sanyo Kokusaku Pal Co., Ltd.) Carplex # 800

(White carbon: brand name of Shionogi & Co., Ltd.)

The above is uniformly mixed and pulverized to make a dry flowable.

[Formulation Example 5] Granules

Compound A of the present invention 0.1 part

Benthite 55.0 copies

Tanolek 44.9 copies

After uniformly mixing and pulverizing the above, a small amount of water is added, the mixture is kneaded with stirring, granulated by an extrusion granulator, and dried to obtain granules.

[Formulation Example 6] wettable powder

Compound A of the present invention-4.775 parts ― One piece PFP 4 3 copies

(Kaolin-based cranes: J-Cright Industry Co., Ltd., trade name) 505

(Anionic surfactant: Toho Chemical Industry Co., Ltd.) Lunox 100 C 3 parts

(Anionic surfactant: Trade name of Toho Chemical Industry Co., Ltd.) Carplex # 80 (anti-caking agent) 2 parts

(White Car Bon: Shionogi & Co., Ltd.)

The above is uniformly mixed and ground to form a wettable powder.

[Formulation Example 7] Milk

Compound A-653 parts of the present invention

Xylene 7 6 parts

Isso Holon 15

Sonore Ponole 3 0 5 X 6

The above are mixed uniformly to form an emulsion

[Formulation Example 8] Flour

Compound A-500 parts of the present invention

Agri-Resolution S — 7 1 1 8 copies (Non-ionic surfactant: Kao Corporation)

Lunox 100 0 0 C 0.5 part

(Anionic surfactant: Trade name of Toho Chemical Industry Co., Ltd.)

% Mouth Detonation water 20 parts

(Thickener: Loan-Poulin Company D name)

Ethylene glycol (antifreeze) 8 parts

28.5 parts of water

Evenly mix the above to make a Floatable

[Formulation Example 9] Granular wettable powder (dry flowable)

Compound B of the present invention-575 parts

No. 10

(Anionic surfactant: Kuraray Soprene Chemical Co., Ltd.

Banix N 5

(Anionic surfactant: Sanyo Kokusaku Pulp Co., Ltd.) Powerplex # 81010

(White carbon: brand name of Shionogi & Co., Ltd.)

The above is uniformly mixed and pulverized to obtain a dry flowable agent.

For use, the above-mentioned wettable powders, emulsions, flowables and granular hydration agents are diluted 50 to 100 times with water to obtain an active ingredient of 1 One one

Spray 100,000 ppm or the active ingredient in a range of 0.001 to 10 kg per hectare (ha).

Next, the usefulness of the compound of the present invention as a herbicide will be specifically described in the following test examples.

[Test Example 1] Herbicidal effect test by soil treatment

Put the sterilized embankment soil in a plastic box 21 cm long, 13 cm wide and 7 cm deep. , Soybeans, soybeans, and corn seeds are sown in spots, covered with 1.5 cm of soil, and the active ingredient content reaches the specified ratio. In this way, it was evenly sprayed on the soil surface with a small spray. As a chemical solution at the time of spraying, a wettable powder appropriately prepared in accordance with the above-described formulation example was used by diluting with water and sprayed over the entire surface. Three weeks after the application of the chemical, the herbicidal effect on crops and various weeds was examined according to the following criteria.

The results are shown in Table 4.

5: Complete withering or suppression of 90% or more

4: 70-90% suppression

3: 40 to 70% reduction

2: Suppression of 20 to 40%

1: 5 to 20% reduction 0: 5% or less suppression

The extent of suppression was determined by visual observation.

The symbols in the table have the following meanings

Ν (Novier), 0 (Ohishinoku), Μ (Mehishoba), Ε (Enokorokuza), S (Soybean), C (Today), Τ (Tomoro) Koshi)

-

(Table 4)

Compound No.Sato (kg / ha) N 〇 M E S C T

A— 1 0. 63 5 5 5 5 0 0 0

A— 4 0. 63 5 5 5 5 0 0 0

A— 6 0. 63 5 5 5 5 0 0 0

A— 10 0. 63 5 5 5 5 0 0 0

A— 1 1 0. 63 5 5 5 5 0 0 0

A-1 2 0.63 5 5 5 5 0 0 0

A— 13 0. 63 5 5 5 5 0 0 0

A— 17 0. 63 4 5 4 5 0 0 0

A— 19 0.63 5 5 5 5 0 0 0

A- 27 0.63 5 5 5 5 0 0 0

A— 34 0. 63 5 5 5 5 0 0 0

A— 44 0. 63 5 5 5 5 0 0 0

A- 7 0.63 5 5 5 5 0 0 0

A-49 0.63 5 5 5 5 0 0 0

A— 50 0.63 5 5 5 5 0 0 0

A— 51 0. 63 5 5 5 5 0 0 0

A— 57 0. 63 5 5 5 5 0 0 0

A— 58 0. 63 5 5 5 5 0 0 0

A— 65 0. 63 5 5 5 5 0 0 0

B— 1 0. 63 5 5 5 5 0 0 0

B-2 0.63 5 5 5 5 0 0 0

B— 4 0. 63 5 5 5 5 0 0 0 [Continued from Table 4] Compound No. Dose (kg / ha) N 〇 MESCT

B-5 0 .6 3 5 5 5 5 0 0 0

B-6 0. 6 3 4 5 5 5 0 0 0

[Test Example 2] Test for weeding effectiveness by pretreatment of weeds under flooded conditions

After putting alluvial soil into the 1/500 al wagon pot, water is added and mixed to make a flooding condition at a depth of 4 cm. After seeds of Nobie and Hoyu were sown in the above pot, rice seedlings at the 2.5 leaf stage were transplanted. One day after sowing, the drug diluent was dropped onto the surface of the water with a mespipet so that the prescribed dose was reached. The pots are placed in a greenhouse at 25 to 30 ° C to grow the plants, and three weeks after the application of the chemical droplets, the herbicidal effect on rice and weeds is determined according to the criteria in Test Example 1. I investigated. Table 5 shows the results.

The symbols in the table have the following meanings.

N (Novier), H (Hoyu Rui), R (Transplanted rice) one

(Table 5)

Compound No. Dose (g / a) N H R

A— 1 1 0 5 5 0

A— 3 1 0 5 5 0

A— 4 1 0 5 5 0

A— 6 1 0 5 5 0 A— 1 0 1 0 5 5 0 A— 1 1 1 0 5 5 0 A-1 2 1 0 5 5 0 A- 1 3 1 0 5 5 0 A— 1 4 1 0 5 5 0 A— 1 5 1 0 5 5 0 A— 1 6 1 0 5 5 0 A—1 7 1 0 5 5 0 A— 1 8 1 0 5 5 0 A-1 9 1 0 5 5 0

A-2 3 1 0 5 5 0

A— 2 5 1 0 5 5 0

A- 2 7 1 0 5 5 0

A- 2 9 1 0 5 5 0 A-3 1 1 0 5 5 0

A- 3 2 1 0 5 5 0

A- 3 4 1 0 5 5 0

A— 3 7 1 0 5 5 0 [Continued from Table 5] Compound.Dose (a) NHR

A- 3 9 1 0 5 0

A— 4 4 1 0 5 0

A— 4 5 1 0 5 0

A- 4 7 1 0 5 0

A— 4 9 1 0 5 0

A-5 0 1 0 5 0 A— 5 1 1 0 5 5 0

A— 5 2 1 0 5 5 0

A— 5 3 1 0 5 5 0

A— 5 4 1 0 5 5 0

A— 5 5 1 0 5 5 0

A- 5 6 1 0 5 5 0

A-5 7 1 0 5 5 0

A- 5 8 1 0 5 5 0

A- 5 9 1 0 5 5 0

A— 6 3 1 0 5 5 0

A— 6 4 1 0 5 5 0

A— 6 5 1 0 5 5 0

Λ— 6 6 1 0 5 5 0

B— 1 1 0 5 5 0

B-2 1 0 5 5 0

B— 3 1 0 5 5 0 [Table 5 continued]

Compound NQ. Dose) N H R

B— 4 1 0 5 5 0 B—5 1 0 5 5 0 B— 6 1 0 5 5 0

Claims

O 94/07857 2 1 —

Equation (11 A) or Equation (B)

Contract

(1-A) (1-B)

0

[Wherein, R ¹ , R ² and R ³ each independently represent a hydrogen atom or a 〇i-c ₄ alkyl group, and X represents an oxygen atom or a sulfur atom. Y represents a halogen atom, C i -C ₄ alkyl group, C

C 4 Alkoxy group, cic ₄ N-alkoxy group or C j

C represents a haloalkoxy group; m is an integer of 0 to 5; and m is an integer of 2 to 5, Y may be the same or different. N represents 1 or 2 and Q represents an optionally substituted heterocyclic ring, an optionally substituted naphthene-lens ring, or an substituted even if good contraction Gofuku ring, was or shea § cyano group to display the C 0 ₂ a (a is a hydrogen atom, _C} ~ C ₄ § Le key Le group or the full We two Le group. ) And Q 'is a permissible permuted vinyl ring, a permissible permuted complex ring, or a permuted naph. Talen rings, condensed compound that may be replaced 94/07857 2 2 ring, was or shea § Roh group represented by the (Table be. Meaning of A before Symbol the same way) C 0 ₂ A. ] The cyclic amide compound represented by these.

2. The cyclic amide compound according to claim 1, represented by the formula (11-A).

3. The ring-bound amide compound according to claim 1, which is represented by the formula (11-B).

4. Q Chikaraku Shi § cyano group, C 0 ₂ A (representing the A is a hydrogen atom, C _t ~ Ji § Ruki Le group or full Yu two Le group.)

i

twenty four

(Wherein, z is C b gain down atom, ~ c ₄ A Le key Le group, ~ c, A Le co key sheet group, C ics ₄ Honoré key Honoré group, 〇丄~ c ₄ necked A Le co key Shi group, c ~ c ₄ A Le key Le Chi O group, ~ c ₄ A Le key ls e le full I d Le group, C j ~ C, § Honoré key ls e Honoré e d Honoré group, two Bok port group A represents a non-reactive carbonyl group, a non-reactive carboxylic group or a holminole group, a represents 0, 1 or 2, and a represents 2 In this case, Z may be the same or different, b represents 0 or 1, and R ⁴ represents a hydrogen atom or a ~ C 'alkyl group. A cyclic amide compound according to claim 2.

5 Q 'force' Shea § cyano group, C 0 ₂ A (A is a hydrogen atom, C

1 C

4 represents an alkyl group or a phenyl group. ), twenty five

O 94/07857 ― _{± 2 γ} ― PCT / JP93 Fine 6

(Wherein, zeta Ha B gain down atom, cic ₄ A Ruki Le group, ci ~ c ^ § Honoré co key sheet group, ~ 〇ヽB A Ruki Le group, ~ c ₄ b A Honoré co key sheet group , ~ c ₄ § Norre key Norre Chi O group, ~ c ₄ A Le key Norre scan Norre full I two Lumpur based, C! ~ 〇 ₄ § Norre key Norre scan Norre host two Norre group, two-door opening group, cic ₄ Represents an alkoxycarbonyl group, a carboxyl group or a halogeno group; a represents 0, 1 or 2; And b represents 0 or 1, and R ⁴ represents a hydrogen atom or a ~ C _/ ! Alkyl group.) Cyclic amide compound.

6. The cyclic amide compound according to claim 4, wherein R ¹ and R ² are each independently represented by a methyl group or an ethyl group.

7. The cyclic amide compound according to claim 5, wherein R ¹ and R ² are each independently represented by a methyl group or an ethyl group.

8. The cyclic amide compound according to claim 6, wherein n is represented by 1.

9. The cyclic amide compound according to claim 6, wherein n is represented by 2.

10. The cyclic amide compound according to claim 7, wherein n is 1.

11. The cyclic amide compound according to claim 7, wherein n is represented by 2.

12. A herbicide comprising the cyclic amide compound according to claim 1 as an active ingredient.

13. Apply a herbicidally effective amount of the cyclic amide compound according to claim 1.

0 ¾ Θ