WO2000050397A1 - Substituted piperidinedione derivatives and herbicide - Google Patents

Abstract

Piperidinedione derivatives represented by general formula (1) (wherein R?1 and R2¿ each represents halogeno, C¿1-6? alkyl, C1-6 alkylsulfonyl, etc.; R?3¿ represents halogeno, C¿1-6? alkyl, etc.; n is 0, 1, or 2; R?4 and R5¿ each represents hydrogen, C¿1-6? alkyl, etc.; R?6 and R7¿ each represents C¿1-6? alkyl or may be bonded to each other to form an alkylene chain; R?8¿ represents hydrogen, C¿1-6? alkyl, etc.; and Z represents optionally substituted amino, phenyl, heterocycle, etc. or salts thereof; and a herbicide containing one or more of these.

Description

 Description Substituted piperidinedione derivatives and herbicides Technical field:

 TECHNICAL FIELD The present invention relates to a substituted piperidine derivative in which a benzoyl group is substituted at the 3-position of piperidine, and a herbicide.

Background art:

 It is described in WO98 / 29412 that a pyrididinedione compound similar to the compound of the present invention has herbicidal activity.

However, the compounds in which n is 1 or more in the above formula and the compounds in which R ⁶ and R ⁷ are not both hydrogen atoms are not specifically described.

 Further, there is no description of a compound in which the 3-position of the benzene ring has a substituent other than a 5-membered heterocyclic group.

Disclosure of the invention:

 The present invention provides: (a) a compound represented by the general formula (1):

[Wherein, R ¹ and R ² each independently represent a nitrogen atom, a cyano group, a halogen atom

, C alkyl group, alkoxy group, C i - represents a ₆ haloalkyl group, C _i-s Al Kiruchio group, an alkyl sulfide alkylsulfonyl group or a C alkylsulfonyl group. -R ³ is a nitro group, a cyano group, a halogen atom, an alkyl group, a C! -E alkoxy group, a C, -haloalkyl group, a Ci-alkylthio group, a C! -Alkylsulfinyl group or a C alkyl Represents a sulfonyl group.

 n represents 0, 1, and 2.

R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, an alkyl group, a C i -haloalkyl group, a C i -alkoxy C alkyl group, an alkylcarbonyloxy C alkyl group, a hydroxy C i- ₆ alkyl Represents a group, and R ⁴ R ⁵ may be taken together to form an alkylene chain having 25 carbon atoms

R ⁶ represents a hydrogen atom, a d- ₆ alkyl group, a hydroxy ₆ alkyl group, or a C! -S haloalkyl group. However, when R ⁶ is a hydrogen atom, n is not 0.

R ⁷ is an alkyl group, human Dorokishi Jii ₆ alkyl group, a Haroaruki group, also, R ⁶ R ⁷ may form a form a connexion alkylene chain having a carbon number of 2 5 a together, made et al R ⁷ may combine with R ⁵ to form a bond or an alkylene chain having 1 to 4 carbon atoms.

R ⁸ represents a hydrogen atom, an alkyl group, C _{2 6} alkenyl, C _{2 6} Arukini Le groups, C haloalkyl group, C 2 haloalkenyl group, C 2 haloalkynyl groups, C t - _e alkoxy group, C _{2 6} alkenyl It represents a ₆ Arukiniruokishi group, C i-ヽRoarukokishi group, c _{2 6} haloalkenyl O alkoxy group, c ₂ヽRoaru Kiniruokishi group - Okishi group, C _2.

Z is formyl group, Moruhori amino group, C i -s alkoxy group, alkoxy C alkoxy group, C ₂ - ₆ alkenyl group, C -! ₆ alkoxycarbonyl group, a di C i -e alkoxymethyl group, di 〇 I ₆ alkylthiomethyl group, an optionally substituted amino group, an optionally substituted phenyl group, an optionally substituted heterocyclic group or a formula C (R ⁹ ) = NR ¹⁰ (where R ⁹ is hydrogen the atom or _d-6 alkyl group, R ¹⁰ is, human Dorokishi group, C -e alkyl group, ds haloalkyl group, C ₂ -! ₆ alkenyl Le group, C ₂ - ₆ haloalkenyl group, C ₂ - ₆ alkynyl group , C ₂ - haloalkynyl groups, C cycloalkyl groups, C i - ₆ alkoxy groups, C i-alkoxy al kill groups, C> - ₆ alkoxy groups, C ₃ - ₈ cycloalkyl O alkoxy groups, C ₂ - Al Keniruokishi group, C ₂ -! (Haloalkenyl O alkoxy group, C ₂ - ₆ Arukiniruokishi group,

C ₂ — S haloalkynyloxy group, optionally substituted amino group, optionally substituted phenyl group, optionally substituted benzyl group, optionally substituted phenyloxy group or optionally substituted Represents a benzyloxy group. ) Represents a group represented by A substituted piperidindione derivative or a salt thereof represented by the formula:

 (b) A herbicide characterized by containing one or more of the substituted piperidinedione derivative represented by the general formula (1) or a salt thereof as an active ingredient.

 Further, in the present invention, in the definition of Z in the general formula (1), the optionally substituted heterocyclic group may be any of the following groups

1 1 -Nノ E' 1 1

1 1 -N no E '1 1

(In the formula, R ¹¹ and R ¹² each independently represent a hydrogen atom, a halogen atom, a -6 alkyl group or an alkoxy group.)

A derivative or salt thereof according to (a), which is a member selected from the group consisting of: and a herbicide containing them as an active ingredient.

Embodiment of the invention:

In the general formula (1), R ¹ and R ² each independently represent a nitro group; a cyano group; a halogen atom such as fluorine, chlorine, or bromine; a methyl, ethyl, propyl, isopropyl, butyl, t - C and butyl - ₆ alkyl group;! main butoxy, et butoxy, Purobokishi, Isopurobokishi, butoxy, t - C alkoxy, such as butoxy Group; Application Benefits Furuorome chill, Application Benefits click Rorome chill, Furuorome Chill, chloromethane Chill, Jifuruorome Chill, dichloroethylene Rorome chill, Application Benefits Furuoroechiru, C such as a pen evening Furuoroechi Le - ₆ haloalkyl group; main Chiruchio, Echiruchio, pro Piruchio Ci-6 alkylthio groups such as, isopropylthio and butylthio; and methylsulfinyl, ethylsulfinyl, propylsulfinyl and isopropylsulfinyl

Represents a C 1-6 alkylsulfinyl group or a C! -6 alkylsulfonyl group such as methylsulfonyl, ethylsulfonyl, propylpyrusulfonyl, and isopropylsulfonyl.

R ³ is a nitro group; a cyano group; a halogen atom such as fluorine, chlorine, and bromine; a _6- alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, and t-butyl; Ci-6 alkoxy groups such as toxic, ethoxy, propoxy, isopropoxy, butoxy, and t-butoxy; trifluoromethyl, trichloromethyl, fluoromethyl, chloromethyl, difluoromethyl, dicyclomethyl Ci-ii haloalkyl groups such as lorometyl, trifluorethyl, pendufluorethyl, etc .; C! -6 alkylthio groups such as methylthio, ethylthio, propylthio, isopropylthio; methyl sulfinyl, ethyl sulfinyl, ! ₆ alkyl sulfide alkylsulfonyl groups - professional Pirusurufi nil, C, such as Lee Sopuro Pirusuru Fi nil Other eyes Chirusuruhoniru, Echiru sulfonyl, professional Pirusuruhoniru, C, such as Lee Sopuro Pirusuruhoniru! — (; Represents an alkylsulfonyl group.

R ⁴ and R ⁵ are each independently a hydrogen atom; a halogen atom such as fluorine, chlorine, or bromine; methyl, ethyl, propyl, isopropyl, butyl, isoptyl, t

—Ci-S alkyl group such as butyl; C such as trifluorethyl, trichloromethyl, fluoromethyl, chloromethyl, dichloromethyl, difluoromethyl, trifluorethyl, pentafluoroethyl, etc. i- ₆ alkyl group; methoxymethyl

, Alkoxy, methoxymethyl, ethoxymethyl, etc.

1-6 alkyl group; Ci- ₆ alkylcarboxyloxy CS alkyl group such as acetyloxymethyl, ethylcarbonyloxymethyl, acetyloxethyl, etc .; hydroxy c such as hydroxymethyl, hydroxypropyl, and hydroxypropyl! one

6 represents an alkyl group. R ⁴ and R ⁵ are joined together to form ethylene, trimethylene, An alkylene chain having 2 to 5 carbon atoms such as tetramethylene and pentamethylene may be formed.

R ⁶ is a hydrogen atom; methylation, Echiru, propyl, i Sopuro pills, heptyl, Lee Seo heptyl, C i alkyl group such as t _ butyl; human Dorokishime chill, heat, such as heat Dorokishe chill Dorokishi C i - ₆ Alkyl group; C ぃ₆ haloalkyl group such as trifluorethyl, trichloromethyl, fluoromethyl, chloromethyl, trimethyl, dichloromethyl, difluoromethyl, trifluorethyl, pendufluorethyl, etc. Represents

R ⁷ is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t

—Alkyl groups such as butyl; hydroxymethyl alkyl groups such as hydroxymethyl and hydroxyshethyl; Represents C i haloalkyl groups such as tyl, trifluoroethyl, and pentafluoroethyl

. R ⁶ and R ⁷ may be taken together to form an alkylene chain having 2 to 5 carbon atoms, such as ethylene, trimethylene, tetramethylene, and pentamethylene. Further, R ⁷ and R ⁵ may be taken together to form a bond or an alkylene chain having 1 to 4 carbon atoms such as methylene, ethylene, trimethylene, and tetramethylene.

R ⁸ is a hydrogen atom, methylation, Echiru, propyl, i Sopuro pills, heptyl, Lee Su Wu chill, t -! C and butyl - alkyl group, vinyl, § Li Le, 2 - C _2, such as butenyl - ₆ alkenyl group, Echiniru, 2 - C ₂ such pro pinyl - ₆ alkynyl group, Application Benefits Furuorome chill, Application Benefits click Rorome chill, Furuorome chill, click Rorome chill, diphenyl Ruorome chill, Jikurorome chill, Application Benefits Furuoroechiru, Pentafuruo Roechiru of any C -! ₆ haloalkyl group, 2 - click Lolo vinyl, 2, 2 - Jifuruoro vinyl, 3 - Kuroroa Li Le, 3, 3 - Jikuroroa Li Le, 2 - Kuroroa Li Le C ₂ such as - ₆ Nono b alkenyl group, 2 - click Roroechiniru, 3 - click b port - 2 - pro pinyl, 3 - Fluorochemical one 2 - pro pinyl C, such as ₂ - ₆ C port alkynyl group, main butoxy, Butoxy, Provo alkoxy, Lee Sopurobokishi, butoxy, t - C I ₆ alkoxy group such as butoxy, bi Niruokishi, 2 - propenyl Niruokishi, § Li Ruokishi, 2 - C Arukeniruokishi group such Buteniruokishi, Echiniruokishi, 2 —C ₂ _ such as propynyloxy 6 alkynyloxy group, ₆ noroalkoxy group, 2-chlorovinyloxy, 2

C ₂ — ₆ haloalkenyloxy groups such as, 2 — difluorovinyloxy, 3 — chloroallyloxy, 3, 3 — dichloroallyloxy, 2 — chloroallyloxy, 2-chloroethynyloxy, 3 _ black port one 2 - propynyl O carboxymethyl, 3 - represents a ₆ haloalkynyl O dimethylvinylsiloxy groups - fluoroalkyl one 2 - C ₂ such as propynyl O alkoxy.

Z is a formyl group; a morpholino group; C! Such as methoxy, ethoxy, propoxy, and isopropoxy. - ₆ alkoxy group;! Main Tokishime butoxy, main Tokishe butoxy, C I ₆ alkoxy C-beta alkoxy group such as E Tokishime butoxy; vinyl, Ryo Lil, 2 - C 2 -6 alkenyl group such as butenyl; main butoxycarbonyl, D- ₁₆ alkoxycarbonyl groups such as ethoxycarbonyl; diCi- ₆ alkoxymethyl groups such as dimethoxymethyl and ethoxymethyl; dialkylthiomethyl groups such as dimethylthiomethyl and ethylthiomethyl; CiS alkyl groups such as methyl and ethyl group, Asechiru, propionyl, alkyl carbonyl group, main Chirusuruhoniru, c Bok _β alkylsulfonyl group such Echirusuruhoniru, methyl § Mi Bruno carbonyl, Echirua Mi Roh carbonyl, Jimechiruami Roh carbonyl, Jefferies Chiruami Bruno carbonyl such Puchiriru A mono- or di-substituted amino group such as a C i -e alkylaminocarbonyl group or a benzyl group; a halogen atom such as cyano, nitrogen, fluorine, chlorine, or bromine at any position; C! -S alkyl groups such as methyl and ethyl, C- _S alkoxy groups such as methoxy and ethoxy, and trifluoromethyl

C, - represents a ₆ haloalkyl group, main butoxycarbonyl, et butoxy C i-S alkoxycarbonyl good full We two Le group which may have a substituent such as groups such as carbonyl. Z represents a saturated or unsaturated 5- to 6-membered heterocyclic group containing 1 to 4 N, 0 or S atoms and optionally having substituents R ¹¹ and R ¹² . This heterocyclic group is bonded to the benzene ring at a carbon atom. Preferred heterocyclic groups include, for example, 2-furyl, 3_furyl, oxazole-2-yl, oxazolu-l 4-yl, oxazolu-l-5-yl, isoxox-l-ru 3 Yl, oxoxazoluru 4 yl, isoxoxazolu — 5 — yl, 1, 2, 4 — oxadiazol — 3 — yl, 1, 2, 4 — oxaziazoluru 5 — yl, 1, 3, 4-Oxaziazol 2-yl, thiazo 1-2-yl, thiazo 1-4-yl, thiazo 1-5 1-yl, isotiazole—3—yl, isotiazole—41—yl, isotizazol—5—yl, s 2,4—thiadiazol—3—yl, s 2, 4—thiaasia Zolulu 5 — yl, 1, 3, 4 — thiadiazole — 2 _ yl, imidazoluu 2 yl, imidazoluru 4 — yl, 2 — chenil, 3 — chenil, pyrazole 3 _yl, pyrazole-4 yl, 1, 2, 4 — Triazol 3 — yl, tetrazole 5 — yl, 4, 5 — dihidroy soxazolu 3 — yl, 4, 5 _dihydroisoxazole-1-4-yl, 4,5-dihydroisoxazole-1 5-1yl, 2-pyridyl, 3-pyridyl, 4-pyridyl and the like. The heterocyclic group may be substituted at any position with a substituent RH, such as a halogen atom such as fluorine, chlorine and bromine, a Ct- ₆ alkyl group such as methyl and ethyl, and an alkoxy group such as methoxy and ethoxy. it may have a R ^12.

 Preferred examples of the heterocyclic group include the following groups.

(In the formula, R ¹¹ and R ¹² each independently represent a hydrogen atom, a halogen atom, an ealkyl group, or a _Ct - ₆ alkoxy group.)

Further, Z represents a group represented by the formula: C (R ⁹ ) = NR ^{1 ()} . R ⁹ represents a hydrogen atom or an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl and t-butyl; a hydroxy group; methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl; C- ₆ alkyl group such as monobutyl; trifluoromethyl, trichloromethyl, fluoromethyl, chloromethyl, Jifuruoromechiru, dichloromethyl, Application Benefits Furuoroechiru, C alkyl group such as penta full O Roe Chi le; vinyl, 1 - propenyl, C ₂ such Ariru, crotyl, blanking evening Jeniru - ₆ alkenyl group; 2 - chloro vinyl, 2 2 - Jifuruoro vinyl, 3 _ chloroallyl, 3, 3 - dichloro allyl, 2 - C ₂ such as chloroallyl - ₆ haloalkenyl group; Echiniru, 1 - propynyl, 2 - C alkynyl group such propynyl; 2 - Kuroroechiniru, 3 - chloro 2 - propynyl, 3 - off Lolo one 2 - C ₂ Roarukiniru group such propynyl; cyclopropyl, C _3, such as cyclo pentyl, cyclohexyl - ₈ cycloalkyl group; main butoxy, et butoxy, Purobokishi, Isopurobokishi, butoxy , t - C ₆ an alkoxy group such as butoxy; main Tokishimechiru Main Tokishechiru, et Tokishimechiru, C physician ₆ alkoxy C physician ₄ alkyl group, such as e Tokishechiru; Application Benefits Furuorome butoxy, 1, 1, 2, 2 - Te Torafuruoroe butoxy, Application Benefits chloromethane butoxy, C such Jifuruorome butoxy, - ₆ haloalkoxy groups; C ₈ cycloalkyl O alkoxy groups such as cyclopropyl O alkoxy, cyclopentyloxy Ruo alkoxy, cyclohexylene Kishiruokishi; Biniruokishi, 1 - pro Bae Niruokishi, Ariruokishi, Kurochiruokishi, C _2, such as porcine Genis Ruo carboxymethyl - e Arukeniruo C2-S haloalkenyloxy groups such as 1-chlorovinyloxy, _2- chlorovinyloxy, 3-chloroallyloxy, and 2-chloromouth crotyloxy; ethinyloxy, 1-propynyloxy, 2— C _2, such as propynyl O carboxymethyl - ₆ Arukiniruokishi group Application Benefits Full O b methyl O alkoxy, 2 - Kuroroechiniru Okishi, 2 - Promo E Hee Ruo carboxymethyl, 3 - Black 2 - propynyl O carboxymethyl, 3, 3, 3 - Application Benefits Furuoro 1 one C ₂ such as propynyl O carboxymethyl - ₆ haloalkynyloxy group; amino group which may be substituted such as methylamino, ethylamino, dimethylamino, getylamino, etc .; phenyl group which may be substituted; benzyl group which may be substituted A phenyloxy group which may be substituted or a benzyloxy group which may be substituted; Here, phenyl, benzyl, Fueniruokishi, is a substituent of Benjiruokishi, fluorine, chlorine, a halogen atom such as bromine; methyl, which C a Echiru - ₆ alkyl group, main butoxy, such as e butoxy C> - _s An alkoxy group; a C haloalkyl group such as trifluoromethyl; a C haloalkoxy group such as trifluoromethoxy; The compound of the present invention can be produced by the following method.

 Manufacturing method (i)

(Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ^e , R ⁷ , R ⁸ , n and Z have the same meanings as described above, and Q is a halogen atom, an alkylcarbonyloxy group Represents an alkoxycarbonyloxy group or a benzoyloxy group.)

 In the above step, the compounds (3a) and (3b) are prepared by mixing 1 mol of the compound (2) with ArC0Q (where Ar and Q have the same meanings as described above) or one of them. It is obtained by using in excess and reacting in the presence of 1 mole or an excess of base.

 Bases used in the reaction include alkali metal hydroxides such as K〇H, Na〇H, alkali metal carbonates such as sodium carbonate and potassium carbonate, and calcium hydroxide. Alkaline earth metal hydroxides such as magnesium hydroxide, alkaline earth metal carbonates such as calcium carbonate, triethylamine, triisopropylamine, and tri (C alkyl) amines such as diisopropylpropylamine. Examples include organic bases such as gin, sodium phosphate, and the like.

Examples of the solvent include water, methylene chloride, chloroform, toluene, and ethyl acetate. Dimethylformamide (DMF), tetrahydrofuran (THF), dimethyloxetane (DME), and acetonitril.

 The reaction mixture is stirred at 0 ° C to 50 ° C until the reaction is completed. The reaction can also be carried out in a two-phase system using a phase transfer catalyst such as a quaternary ammonium salt. Further, the compounds (3a) and (3b) are obtained by converting the compound (2) and the compound ArC00H (Ar represents the same meaning as described above) with a dicyclohexylcarbodiimide (DCC )) In the presence of a dehydrating condensing agent. As the solvent used in the reaction with DCC, etc., methylene chloride, chloroform, toluene, ethyl acetate, DMF, THF, DME, acetonitrile and the like are used. The reaction mixture is stirred at −10 ° C. to 50 ° C. until the reaction is completed. The reaction mixture is worked up in a conventional manner.

 Compounds (3a) and (3b) are used as a mixture in the next rearrangement reaction. The rearrangement reaction is performed in the presence of a cyanide and a mild base. That is, one mole of the compounds (3a) and (3b) is replaced by 1 to 4 moles of base, preferably 1 to 2 moles of base and 0.01 to 1.0 moles, preferably Is to obtain the compound (1a) by reacting with 0.05 to 0.2 mol of a cyanide compound. As the base used here, any of the above bases can be used. Further, as the cyanide compound, potassium cyanide, sodium cyanide, acetate cyanide hydride, hydrogen cyanide, a polymer holding potassium cyanide, and the like are used. The reaction is completed in a shorter time by adding a small amount of a phase transfer catalyst such as crown ether. The reaction is carried out at a temperature lower than 80 ° C, preferably at 20 to 40 ° C. The solvents used are 1,2-dichloroethane, toluene, acetonitrile, methylene chloride, ethyl acetate, DMF, methyl isoptyl ketone, THF, DME, and the like.

 Compound (la) is prepared by reacting compound (2) with ArCoCN (Ar represents the same meaning as described above) in the presence of a base and, if necessary, a Lewis acid according to the following method. It can also be obtained.

Bases used are alkali metal hydroxides such as KOH and NaOH, hydroxides of alkaline earth metals such as magnesium hydroxide and calcium hydroxide, and triethyl. § Mi emissions, Application Benefits such as diisopropyl Sopuro Piruechirua Mi emissions (C -! ₆ alkyl) § Mi emission, organic bases such as pin lysine, carbonate Na Application Benefits um, and the like phosphate Na Application Benefits um. Suitable Lewis acids include zinc chloride, aluminum trichloride and the like, preferably zinc chloride.

 The reaction is carried out in an organic solvent such as acetonitril and methylene chloride at a suitable temperature from 120 ° C to the boiling point of the solvent. Manufacturing method (ii)

化合物 （ 1 c ) は、 化合物 （ l b) (式中、 R¹³は、 低級の分岐していてもよ いアルコキシ、 ァラアルキルォキシ、 またはァセ トキシを意味する。 ） を、 塩素 、 臭化水素酸などのハロゲン化水素酸， ト リ フルォロ酢酸， 三臭化ホウ素などと の反応、 水素化分解あるいはアルカ リ加水分解などにより、 また必要に応じて、 次いで加水分解を行う ことによって製造することができる。

The compound (1c) is a compound (lb) (wherein R ¹³ represents a lower branched alkoxy, araalkyloxy, or acetoxy), and chlorine, odor or the like. Manufactured by reaction with hydrohalic acids such as hydrofluoric acid, trifluoroacetic acid, boron tribromide, etc., by hydrogenolysis or alkaline hydrolysis, and, if necessary, by subsequent hydrolysis be able to.

 Further, the compound (1c) is converted into a compound (Id) (L is a leaving group by subjecting the compound to a halogenation, alkylsulfonation or arylsulfonation by an ordinary method. Logen, alkylsulfonate, arylsulfonate, etc.).

Further, the compound (1e) is obtained by converting the compound (Id) into a In the presence, from −20 to the boiling point of the solvent used, preferably from room temperature to 100,

It can be produced by reacting from 30 minutes to several 10 hours.

 The base used is an alkali metal hydroxide such as KOH or NaOH, a hydroxide of an alkaline earth metal such as magnesium hydroxide or calcium hydroxide, triethylamine, diisopropylamine. Tri (C! — (; Alkyl) amine, pyridine, 1,8—diazabicyclo [5.4.0] デ decene-1 7 (DBU), t—Bu0K, Triton B, sodium carbonate and sodium phosphate.

 The solvents used, alone or in combination, include water, alcohol, methylene chloride, benzene, toluene, ethyl acetate, DMF, THF, DME, and acetonitrile.

 The above A r C 0 Q (A r and Q have the same meaning as described above) and A r C CH (A r has the same meaning as described above) are to be produced according to a known method. Can be.

 The cyclic dione compound represented by the general formula (2) can be produced according to the following route.

base

(Wherein, R ⁵ , R ⁶ , R ⁷ and R ⁸ represent the same meaning as described above, and R ⁴ represents a group shown in the figure. R ¹⁴ and R ¹⁵ represent a lower alkyl group; Y represents a halogen atom Represent. )

The compound (6) is equimolar or in excess of the compound (5) obtained by a known method from the compound (4) and R ⁸ NH ₂ (where R ⁸ has the same meaning as described above). (in here, R ¹⁵ is the same as the table to.) acid chloride Li de R ¹⁵ 0 ₂ CCHCOC 1 Te cowpea and the solvent, an equimolar or, in the reaction in the presence of excess base can get.

 The base used is an alkali metal hydroxide such as KOH or NaOH, an alkali metal carbonate such as sodium carbonate or potassium carbonate, or an alkali metal such as calcium hydroxide or magnesium hydroxide. Alkaline earth metal hydroxides, calcium carbonate and other alkaline earth metal carbonates, triethylamine, diisopropylethylamine and other tri (C alkyl) amines, pyridines and other organic compounds Bases, sodium phosphate and the like. Solvents used include methylene chloride, chloroform, toluene, ethyl acetate, DMF, THF, DME, and acetonitrile.

 The reaction is carried out between 110 ° C. and the boiling point of the solvent used.

 Then, the obtained compound (6) was converted to an organic compound in the presence of a base of an equimolar to triple alkali metal alcoholate such as sodium ethylate or a metal hydride such as sodium hydride. The compound (7) is obtained by reacting in a solvent at a temperature between 0 ° C and the boiling point of the solvent, followed by neutralization with an inorganic acid such as hydrochloric acid.

 Here, examples of the solvent used for the reaction include alcohols such as ethanol and methanol, ethers such as THF and DME, hydrocarbons such as toluene and xylene, and DMF. .

 By heating the obtained compound (7) in a solvent in the presence of water, the compound (7)

2a) is obtained.

 Solvents used include methylene chloride, chloroform, toluene, ethyl acetate, DMF, THF, dioxane, DME, and acetonitrile.

Further, the compound (2b) can be prepared by reacting the compound (2a) in a solvent in the presence of a base in the presence of a base, and the electrophilic reagent R ⁴ Y (where R ⁴ represents a group shown in the figure; Y represents a halogen atom.) And —78 ° C. to the boiling point of the solvent used. _ Solvents used are ether, THF, benzene, toluene and hexane. Examples of the base to be used include alkyl lithium, lithium diisopropylamide and the like.

 Acrylic acid derivatives, benzoic acid ester aldehydes and intermediates thereof, benzoic acid ester carboxylic acids and intermediates thereof, intermediates having a heterocyclic ring, etc. of compound (4) used as raw materials Can be produced by a known method described in, for example, W098 / 29412, W098 / 56676, and JP-A-10-338675.

 When the compound (1) contains a free hydroxyl group by the above-mentioned method, a salt thereof, particularly an agriculturally and horticulturally acceptable salt, enamine or an analog thereof, or an acylate may be prepared from the compound. , Sulfonates and carbamates can induce ethers, polyesters, sulfoxides or sulfones. Suitable agriculturally and horticulturally acceptable salts include salts of sodium, calcium, calcium and ammonium.

Examples of ammonium salts include those of the formula: N ⁺ R a R b R c R d (where R a, R b, R c and R d are each independently hydrogen and optionally a hydroxy group , Which is an alkyl group). R a, R b, 1 (: 1 and 1 (1 is an optionally substituted alkyl group, these may contain 1 to 4 carbon atoms. Desirable.

 Suitable enamines or analogs thereof are those in which each of the 部分 H moieties is of the formula: — NR e R f (where the shaku 6 ぉ! Is independently hydrogen or, for example, having 1 to 6 carbon atoms. , Halogen, S (0) gRh (where Rh is, for example, 1 to 6 carbon atoms), optionally substituted alkyl or aryl groups such as phenyl groups. Is an optionally substituted alkyl or aryl group, for example a phenyl group, and g represents 0 to 2.).

Suitable acylate, ether or olebamate derivatives are those in which the OH moiety has the formula: —〇C ORi, one ORj or one OCONR k R l, where R i and R j Has the same meaning as Rh described above, and Rk and R1 have the same meanings as Re described above.) These derivatives can be produced by ordinary synthetic chemistry techniques. The compound (1) of the present invention and the starting compounds (2), (7) and the like may have optically active isomers in addition to a number of tautomeric forms such as those shown below. May exist. All such forms are included in the scope of the present invention.

本発明化合物、 反応終了後、 通常の後処理を行う ことにより目的物を得ること ができる。 Ar =

The target compound can be obtained by subjecting the compound of the present invention to a usual post-treatment after the reaction.

 The structure of the compound of the present invention was determined from IR, NMR, MS and the like. Representative examples of the compound of the present invention are shown in Tables 1 and 2.

The abbreviations (A to R) in column の of these tables represent the following meanings, and Ph represents a phenyl group. OAV / Li dfl one

5 o :,

 〇

PQ: One

 O o

:- twenty five-

<σ

N 0 R ³ n

(つづき）

(Continued)

第 1 表 （つづき）

Table 1 (continued)

(つづき）

(Continued)

ΐ ζ

ΐ ζ

 (^ c) Halla ΐ

f / IDd m 6 £ 0S / 00 OM Table 1 (continued)

(つづき）

(Continued)

(つづき）

(Continued)

(つづき）

(Continued)

(つづき）

(Continued)

D 1 n 2 R ^d nn R 4

K ⁴ R ⁵ R ⁶ R ⁷ R ⁸ Z

CI SO2CH3 n = 0 HH CH ₃ CH ₃ CH ₃ CH (0CH ₃ ) ₂

CH ₃ SO2CH3 n = 0 HH CH ₃ CH ₃ H CH (0CH ₃ ) ₂

CH ₃ SO2CH3 n = 0 HH CH ₃ CH ₃ CH ₃ CH (0CH ₃ ) ₂

CI CI n = 0 HH CH ₃ CH ₃ H CH (0CH ₃ ) ₂

CI SO2CH3 n = 0 HH CH ₃ CH ₃ H NH ₂

CI SO2CH3 n = 0 HH CH ₃ CH ₃ CH ₃ NH ₂

CH ₃ SO2CH3 n = 0 HH CH ₃ CH ₃ H NH ₂

CH ₃ SO2CH3 n = 0 HH CH ₃ CH ₃ CH ₃ NH ₂

CI CI n = 0 HH CH ₃ CH ₃ CH ₃ NH ₂

CI SO2CH3 n = 0 HH CH ₃ CH ₃ H NHCH3

CI SO2CH3 n = 0 HH CH ₃ CH ₃ CH ₃ NHCH ₃

CH ₃ S0 ₂ CH ₃ n = 0 HH CH ₃ CH ₃ H NHCH ₃

CH ₃ S0 ₂ CH ₃ n = 0 HH CH ₃ CH ₃ CH ₃ NHCH ₃

CI CI n = 0 HH CH ₃ CH ₃ H NHCH3

CI SO2CH3 n = 0 HH CH ₃ CH ₃ HN (CH ₃ ) ₂

CI SO2CH3 n = 0 HH CH ₃ CH ₃ CH ₃ N (CH ₃ ) ₂

CH ₃ S0 ₂ CH ₃ n = 0 HH CH ₃ CH ₃ HN (CH ₃ ) ₂

CH ₃ SO2CH3 n = 0 HH CH ₃ CH ₃ CH ₃ N (CH ₃ ) ₂

CI CI n = 0 HH CH ₃ CH ₃ CH ₃ N (CH ₃ ) ₂

CI SO2CH3 n = 0 HH CH ₃ CH ₃ H NHCOCH3

CI SO2CH3 n = 0 HH CH ₃ CH ₃ CH ₃ NHCOCH3

CH ₃ SO2CH3 n = 0 HH CH ₃ CH ₃ H NHCOCH3

CH ₃ SO2 CH3 n = 0 HH CH ₃ CH ₃ CH ₃ NHCOCH3

CI CI n = 0 HH CH ₃ CH ₃ H NHCOCH3

CI SO2CH3 n = 0 HH CH ₃ CH ₃ H NHCOOCH3 (Continued)

R ¹ R ² R ³ n R ⁴ R ⁵ R ⁶ R ⁷ R ⁸ Z

CI SO2CH3 n = 0 HH CH ₃ CH ₃ CH ₃ NHCOOCH3

CH ₃ SO2CH3 n-0 HH CH ₃ CH ₃ H NHCOOCH3

CH ₃ SO2CH3 n = 0 HH CH ₃ CH ₃ CH ₃ NHCOOCH3

CI CI n = 0 HH CH ₃ CH ₃ CH ₃ NHCOOCH3

CI S0 ₂ CH ₃ n = 0 HH CH ₃ CH ₃ HN (CH ₃ ) COOCH ₃

CI S0 ₂ CH ₃ n = 0 HH CH ₃ CH ₃ CH ₃ N (CH ₃ ) C00CH ₃

CH ₃ SO2CH3 n = 0 HH CH _S CH ₃ HN (CH ₃ ) C00CH ₃

CH ₃ S0 ₂ CH ₃ n-0 HH CH ₃ CH ₃ CH ₃ N (CH ₃ ) C00CH ₃

CI CI n = 0 HH CH ₃ CH ₃ HN (CH ₃ ) C00CH ₃

CI SO2CH3 n = 0 HH CH ₃ CH ₃ H NHS0 ₂ CH ₃

CI S0 ₂ CH ₃ n = 0 HH CH ₃ CH ₃ CH ₃ NHS0 ₂ CH ₃

CH ₃ SO2CH3 n = 0 HH CH ₃ CH ₃ H NHSO2CH3

CH ₃ S0 ₂ CH ₃ n = 0 HH CH ₃ CH ₃ CH ₃ NHS0 ₂ CH ₃

CI CI n = 0 HH CH ₃ CH ₃ CH ₃ NHSO2CH3

CI SO2CH3 n = 0 HH CH ₃ CH ₃ H NHC0N (C ₂ H ₅ ) ₂

CI S0 ₂ CH ₃ n = 0 HH CH ₃ CH ₃ CH ₃ NHC0N (C ₂ H ₅ ) ₂

CH ₃ SO2CH3 n = 0 HH CH ₃ CH ₃ H NHC0N (C ₂ H ₅ ) ₂

CH ₃ SO2CH3 n = 0 HH CH ₃ CH ₃ CH ₃ NHC0N (C ₂ H ₅ ) 2

CI CI n = 0 HH CH ₃ CH ₃ H NHC0N (C ₂ H ₅ ) ₂

CI S0 ₂ CH ₃ n = 0 HH CH ₃ CH ₃ H NHCH ₂ Ph

CI SO2CH3 n = 0 HH CH ₃ CH ₃ CH ₃ NHCH ₂ Ph

CH ₃ S0 ₂ CH ₃ n = 0 HH CH ₃ CH ₃ H NHCH ₂ Ph

CH ₃ S0 ₂ CH ₃ n = 0 HH CH ₃ CH ₃ CH ₃ NHCH ₂ Ph

CI CI n-0 HH CH ₃ CH ₃ CH ₃ NHCH ₂ Ph

CI S0 ₂ CH ₃ n = 0 HH CH ₃ CH ₃ H Ph (Continued)

(つづき）

(Continued)

R ¹ R ² R ³ n R ⁴ R ⁵ R ⁸ Z

CI SO2CH3 n-0 HH CH ₃ CH ₃ CH ₃ Ph-3-CI

CH ₃ SO2CH3 n = 0 HH CH ₃ CH ₃ H Ph- 3-CI

CH ₃ S0 ₂ CH ₃ n = 0 HH CH ₃ CH ₃ CH ₃ Ph-3- CI

CI CI n = 0 HH CH ₃ CH ₃ CH ₃ Ph- 3- CI

CI S0 ₂ CH ₃ n = 0 HH CH ₃ CH ₃ H Ph- 4- CI

CI S0 ₂ CH ₃ n = 0 HH CH ₃ C2 H5 H Ph- 4- CI

CI S0 ₂ CH ₃ n = 0 HH C2H5 C2H0 H Ph-4-Cl

CI S0 ₂ CH ₃ n = 0 HH CH ₃ CH ₃ CH ₃ Ph- 4- CI

CI S0 ₂ CH ₃ n = 0 HH CH ₃ C2H5 CH ₃ Ph- 4- CI

CI SO2CH3 n = 0 HH C2 H5 C 2 H5 CH ₃ Ph- 4- CI

CH ₃ SO2CH3 n = 0 HH CH ₃ CH ₃ H Ph-4-CI

CH ₃ SO2CH3 n = 0 HH CH ₃ C2H5 H Ph-4-Cl

CH ₃ S0 ₂ CH ₃ n = 0 HH C2 H5 C 2 Ho H Ph-4-Cl

CH ₃ SO2 CH3 n = 0 HH CH ₃ CH ₃ CH ₃ Ph-4-Cl

CH ₃ S0 ₂ CH ₃ n = 0 HH CH ₃ C2 H5 CH ₃ Ph-4-Cl

CH ₃ S0 ₂ CH ₃ n = 0 HH C2H5 C2 H5 CH ₃ Ph- 4- CI

CI CI n = 0 HH CH ₃ CH ₃ H Ph-4- CI

CI CI n = 0 HH CH ₃ C2H5 H Ph- 4- CI

CI CI n = 0 H H C2H5 C2H5 H Ph-4-CI

CI CI n = 0 HH CH ₃ CH ₃ CH ₃ Ph-4-CI

CI CI n-0 HH CH ₃ C2H5 CH ₃ Ph-4-Cl

CI CI n = 0 HH C2H5 C2H5 CH ₃ Ph-4-Cl

CI SO2CH3 n = 0 H H-(CH 2) 2-H Ph- 4- CI

CH ₃ S0 ₂ CH ₃ n = 0 HH-(CH 2) 2-CH ₃ Ph- 4- CI

CI CI n = 0 HH-(CH 2) 2-H Ph-4-CI Table 1 (continued)

R ¹ R ² R ³ n R ⁴ R ⁵ R ⁶ R ⁷ R ⁸ Z

CI SO2CH3 n = 0 HH-(CH 2) 4-CH ₃ Ph- 4- CI

CH ₃ SO2CH3 n = 0 HH-(CH 2) 4 "H Ph-4-Cl

CI CI n = 0 H H-(CH 2) 4-H Ph- 4-CI

CH ₃ 0 S0 ₂ CH ₃ n = 0 HH CH ₃ CH ₃ H Ph-4- CI

CH3O SO2CH3 n = 0 HH CH ₃ CH ₃ CH ₃ Ph-4-Cl

CI SO2CH3 n = 0 HH CH ₃ CH ₃ H Ph-2-CH ₃

CI SO2CH3 n = 0 HH CH ₃ CH ₃ CH ₃ Ph-2-CH ₃

CH ₃ SO2CH3 n = 0 HH CH ₃ CH ₃ H PI1-2-CH3

CH ₃ SO2CH3 n = 0 HH CH ₃ CH ₃ CH ₃ Ph-2-CH ₃

CI CI n = 0 HH CH ₃ CH ₃ CH ₃ Ph-2-CH ₃

CI SO2CH3 n = 0 HH CH ₃ CH ₃ H Ph-4-CH ₃

CI SO2 CH3 n-0 HH CH ₃ CH ₃ CH ₃ PI1-4-CH3

CH ₃ SO2CH3 n = 0 HH CH ₃ CH ₃ H Ph-4-CH ₃

CH ₃ SO2CH3 n = 0 HH CH ₃ CH ₃ CH ₃ Ph-4- CH ₃

CI CI n = 0 HH CH ₃ CH ₃ H Ph-4-CH ₃

CI SO2CH3 n = 0 HH CH ₃ CH ₃ H Ph-4-CN

CI SO2CH3 n = 0 HH CH ₃ CH ₃ CH ₃ Ph-4-CN

CH ₃ SO2CH3 n = 0 HH CH ₃ CH ₃ H Ph-4-CN

CH ₃ SO2CH3 n = 0 HH CH ₃ CH ₃ CH ₃ Ph-4-CN

CI CI n = 0 HH CH ₃ CH ₃ CH ₃ Ph-4-CN

_{CI SO2CH3 n = 0 HH CH 3} CH 3 H Ph-4-N0 2

_{CI SO2CH3 n = 0 HH CH 3} CH 3 CH 3 Ph-4-N0 2

_{CH 3 SO2CH3 n = 0 HH CH} 3 CH 3 H Ph - 4- N0 2

CH ₃ S0 ₂ CH ₃ n = 0 HH CH ₃ CH ₃ CH ₃ Ph-4-N0 ₂

_{CI CI n = 0 HH CH 3} CH 3 H Ph-4-N0 2 Table 1 (continued)

R ¹ R ² R ³ n R ⁴ R ⁵ R ⁶ R ⁷ R ⁸ Z

CI SO2CH3 n = 0 HH CH ₃ CH ₃ H Ph-3-CF ₃

CI SO2CH3 n = 0 HH CH ₃ CH ₃ CH ₃ Ph-3-CFs

CH ₃ SO2CH3 n = 0 HH CH ₃ CH ₃ H Ph-3-CF ₃

CH ₃ SO2CH3 n = 0 HH CH ₃ CH ₃ CH ₃ Ph-3-CF ₃

CI CI n = 0 HH CH ₃ CH ₃ CH ₃ Ph-3-CF ₃

CI S0 ₂ CH ₃ n = 0 HH CH ₃ CH ₃ H Ph-3-0CH ₃

CI SO2CH3 n = 0 HH CH ₃ CH ₃ CH ₃ Ph-3-0CH ₃

CH ₃ SO2CH3 n = 0 HH CH ₃ CH ₃ H Ph-3-0CH ₃

CH ₃ SO2CH3 n = 0 HH CH ₃ CH ₃ CH ₃ Ph-3-0CH ₃

CI CI n = 0 HH CH ₃ CH ₃ H Ph-3-0CH ₃

CI SO2CH3 n = 0 HH CH ₃ CH ₃ H Ph-4-C00CH ₃

CH ₃ SO2CH3 n = 0 HH CH ₃ CH ₃ CH ₃ Ph-4-C00CH ₃

CI CI n = 0 HH CH ₃ CH ₃ CH ₃ Ph-4-C00CH ₃

CI S0 ₂ CH ₃ n = 0 HH CH ₃ CH ₃ H Ph-2, 4-CI2

CI SO2CH3 n = 0 HH CH ₃ CH ₃ CH ₃ Ph-2, 4-CI2

CH ₃ SO2CH3 n = 0 HH CH ₃ CH ₃ H Ph-2, 4-C

CH ₃ SO2CH3 n = 0 HH CH ₃ CH ₃ CH ₃ Ph-2, 4-Cl ₂

CI CI n = 0 HH CH ₃ CH ₃ H Ph-2, 4-CI2

CI SO2CH3 n = 0 HH CH ₃ CH ₃ H Ph-2, 5-Cl ₂

CI SO 2 CH 3 n = 0 HH CH ₃ CH ₃ CH ₃ Ph-2, 5-Cl ₂

CH ₃ S0 ₂ CH ₃ n = 0 HH CH ₃ CH ₃ H Ph-2, 5-C

CH ₃ S0 ₂ CH ₃ n = 0 HH CH ₃ CH ₃ CH ₃ Ph-2, 5-C

CI CI n = 0 HH CH ₃ CH ₃ CH ₃ Ph-2, 5-Ch

CI S0 ₂ CH ₃ n = 0 HH CH ₃ CH ₃ H Ph-2, 6-Cl ₂

CI SO2CH3 n = 0 HH CH ₃ CH ₃ CH ₃ Ph-2, 6-C

CH ₃ SO2CH3 n = 0 HH CH ₃ CH ₃ H Ph-2, 6-CI2 Table 1 (continued)

R ² R ³ n R ⁴ R ⁵ R ⁶ R ⁷ R ⁸ Z

CH ₃ S0 ₂ CH ₃ n = 0 HH CH ₃ CH ₃ CH ₃ Ph-2, 6-CI2

CI CI n = 0 HH CH ₃ CH ₃ H Ph-2, 6-Cl ₂

CI SO2CH3 n = 0 HH CH ₃ CH ₃ H Ph- 3, 4-CI2

CI S0 ₂ CH ₃ n = 0 HH CH ₃ CH ₃ CH ₃ Ph-3, 4-C "

CH ₃ S0 ₂ CH ₃ n = 0 HH CH ₃ CH ₃ H Ph-3, 4-Cl ₂

CH ₃ SO2CH3 n = 0 HH CH ₃ CH ₃ CH ₃ Ph-3, 4-Cl ₂

CI CI n = 0 HH CH ₃ CH ₃ CH ₃ Ph- 3, 4-C

CI SO2CH3 n = 0 HH CH ₃ CH ₃ H Ph- 3, 5-C

CI SO2CH3 n = 0 HH CH ₃ CH ₃ CH ₃ Ph- 3, 5-Cl ₂

CH ₃ SO2CH3 n = 0 HH CH ₃ CH ₃ H Ph- 3, 5-Ch

CH ₃ S0 ₂ CH ₃ n = 0 HH CH ₃ CH ₃ CH ₃ Ph- 3, 5-Ch

CI CI n = 0 HH CH ₃ CH ₃ H Ph- 3, 5-Cl ₂

CI SO2CH3 n = 0 HH CH ₃ CH ₃ H Ph-2, 3, 4-Ch

CI SO2CH3 n = 0 HH CH ₃ CH ₃ CH ₃ Ph-2, 3, 4-CI3

CH ₃ S0 ₂ CH ₃ n = 0 HH CH ₃ CH ₃ H Ph-2, 3, 4-CI3

CH ₃ SO2CH3 n = 0 HH CH ₃ CH ₃ CH ₃ Ph-2, 3, 4-Ch

CI SO2CH3 n = 0 HH CH ₃ CH ₃ CH ₃ Ph-4-C00CH ₃

CH ₃ SO2CH3 n = 0 HH CH ₃ CH ₃ H Ph-4-C00CH ₃

CI CI n = 0 HH CH ₃ CH ₃ CH ₃ Ph-2, 3, 4-Ch

CI SO2CH3 n-0 HH CH ₃ CH ₃ H Ph-2, 4, 6-CI3

CI SO2CH3 n = 0 HH CH ₃ CH ₃ CH ₃ Ph-2, 4, 6-C

CH ₃ SO2CH3 n = 0 HH CH ₃ CH ₃ H Ph-2, 4, 6-Ch

CH ₃ SO2CH3 n = 0 HH CH ₃ CH ₃ CH ₃ Ph-2, 4, 6-Cl ₃

CI CI n = 0 HH CH ₃ CH ₃ H Ph-2, 4, 6-C

CI S0 ₂ CH ₃ n = 0 HH CH ₃ CH ₃ H CH = NCH ₃

CI S0 ₂ CH ₃ n = 0 HH CH ₃ CH ₃ CH ₃ CH = NCH ₃ (Continued)

(つづき）

(Continued)

g ε

Z90l0 / 00df / XDd 6S0S / 00 OM 2 Table (continued)

(つづき）

(Continued)

(つづき）

(Continued)

(つづき）

(Continued)

(つづき）

(Continued)

(つづき）

(Continued)

第 2 表 （つづき）

Table 2 (continued)

(つづき）

(Continued)

EC

Table 2 (continued)

R ¹ R ² R ³ n R ⁴ R ⁷ R ⁸ Z

CI SO2CH3 n = 0 H CH ₃ H Ph-2, 5-Ch

CI SO2CH3 n-0 H CH ₃ CH ₃ Ph-2, 5-Cl ₂

CH ₃ SO2CH3 n = 0 H CH ₃ H Ph-2, 5-Cl ₂

CH ₃ SO2CH3 n = 0 H CH ₃ CH ₃ Ph-2, 5-Cl ₂

CI CI n = 0 H CH ₃ H Ph-2, 5-Ch

CI SO2CH3 n = 0 H CH ₃ H Ph-2, 6-C

CI SO2CH3 n = 0 H CH ₃ CH ₃ Ph-2, 6-Cl ₂

CH ₃ S0 ₂ CH ₃ n = 0 H CH ₃ H Ph-2, 6-Ch

CH ₃ SO2CH3 n = 0 H CH ₃ CH ₃ Ph-2, 6-CI2

CI CI n = 0 H CH ₃ CH ₃ Ph-2, 6-C "

CI SO2CH3 n = 0 H CH ₃ H Ph-3, 4-C

CI S0 ₂ CH ₃ n = 0 H CH ₃ CH ₃ Ph-3, 4-Cl ₂

CH ₃ SO2CH3 n = 0 H CH ₃ H Ph-3, 4-Ch

CH ₃ SO2CH3 n = 0 H CH ₃ CH ₃ Ph-3, 4-C "

CI CI n = 0 H CH ₃ H Ph-3, 4-Cl ₂

CI SO2CH3 n = 0 H CH ₃ H Ph-3, 5-Cl ₂

CI SO2CH3 n = 0 H CH ₃ CH ₃ Ph-3, 5-CI2

CH ₃ SO2CH3 n = 0 H CH ₃ H Ph-3, 5-Cl ₂

CH ₃ SO2CH3 n = 0 H CH ₃ CH ₃ Ph-3, 5-CI2

CI CI n = 0 H CH ₃ CH ₃ Ph-3, 5-C "

CI SO2CH3 n = 0 H CH ₃ H Ph-2, 3, 4-Ch

CI S0 ₂ CH ₃ n = 0 H CH ₃ CH ₃ Ph-2, 3, 4-Ch

CH ₃ S0 ₂ CH ₃ n = 0 H CH ₃ H Ph-2, 3, 4-Ch

CH ₃ S0 ₂ CH ₃ n = 0 H CH ₃ CH ₃ Ph-2, 3, 4-Ch

CI CI n = 0 H CH ₃ H Ph-2, 3, 4-Ch

CI SO2CH3 n = 0 H CH ₃ H Ph-2, 4, 6-Ch Table 2 (continued)

(つづき）

(Continued)

_ [Herbicide]

 The herbicide of the present invention contains one or more of the compounds of the present invention as an active ingredient. When the compound of the present invention is actually applied, it can be used in a pure form without adding other components, or in a form that can be taken by a general pesticide for the purpose of using it as a pesticide, ie, hydrating agents, granules. It can be used in the form of powders, powders, emulsions, aqueous solvents, suspensions, flowables, etc. When solid additives are used as additives and carriers, plant powders such as soybean flour and barley flour, diatomaceous earth, apatite, gypsum, talc, bentonite, pyrophyllite, clay, etc. Organic and inorganic compounds such as mineral fine powder, sodium benzoate, urea and sodium sulfate are used. For liquid dosage forms, petroleum fractions such as kerosene, xylene and sorbent naphtha, cyclohexane, cyclohexanone, DMF, DMS0, alcohol, acetate, trichloroethylene, methylisobutyl butyl Use tons, mineral oils, vegetable oils, water, etc. as solvents. Surfactants can be added, if necessary, to obtain a uniform and stable form in these preparations. The surfactant is not particularly limited. Examples of the surfactant include alkylphenyl ether to which polyoxyethylene is added, alkyl ether to which polyoxyethylene is added, higher fatty acid ester to which polyoxyethylene is added, and polyoxyethylene. Nonionic surfactants such as added sorbynyl higher fatty acid esters, polyoxyethylene-added tristylylphenyl ether, etc., sulfate esters of alkylphenyl ethers added with polyoxyethylene, alkylbenzene sulfonates , Higher alcohol sulfates, alkyl sulfates, alkyl naphthalene sulfonates, polycarboxylates, lignin sulfonates, formaldehyde condensates of alkyl naphthalene sulfonates, isobutylene-maleic anhydride Heavy And the like.

 The active ingredient concentration in the herbicide of the present invention varies depending on the form of the preparation described above. For example, in a wettable powder, 5 to 90% by weight (hereinafter simply referred to as%), preferably 10 to 85%: In an emulsion, 3 to 70%, preferably Or 5 to 60%: In granules, a concentration of 0.01 to 50%, preferably 0.05 to 40% is used.

The wettable powder and emulsion thus obtained are diluted to a predetermined concentration with water to form a suspension. As an emulsion or as an emulsion, the granules are directly sprayed or mixed before or after germination of the weeds. In actually applying the herbicide of the present invention, an appropriate amount of 0.1 g or more of the active ingredient is applied per hectare.

 Further, the herbicide of the present invention can be used by mixing with known fungicides, insecticides, acaricides, herbicides, plant growth regulators, fertilizers, and the like. In particular, it is possible to reduce the amount of drug used by mixing and using herbicides. In addition to saving labor, synergistic action of the mixed drugs can be expected to have even higher effects. In that case, a combination with a plurality of known herbicides is also possible.

Suitable agents to be used in combination with the herbicide of the present invention include anilide herbicides such as diflufenican and propanil, and mouth-lowacetarilide herbicides such as arachlor and pretilachlor, and 2,4-D , 2, 4 — Aryloxy alkanoic acid herbicides such as DB, aryloxy phenoxy alkanoic acid herbicides such as diclohop-methyl, phenoxaprop-ethyl, alkaryl carboxylic acids such as dicampa, pyrithiobac Acid herbicides, imidazolinone herbicides such as imazaquin and imazethapyr, urea herbicides such as didurone and isoprolone, carbamate herbicides such as chlorprofam and phenmedifam, and thiocarbamate such as tiobencalp and EPTC. Di-herbicides, trifluralin, pendimethalin, etc. Roaniline herbicides, diphenyl ether herbicides such as acifluorfen, fomesaphane, etc., sulfonyl-rare herbicides such as bensulfuron-methyl and nicosulfuron, metribudine, metamitron, etc. Triazinone herbicides, triazine herbicides such as atrazine and cyanadine; triazopyrimidine herbicides such as flumeram; ditribyl herbicides such as promoxinil and diclobenyl; glyphosate Phosphoric acid herbicides such as glyphosinate, quaternary ammonium salt herbicides such as paracoat and difuenzo coat, and cyclic imid herbicides such as flumichlorack-pentyl and fluthiacet-methyl , And others, isoxavene, ethomethate, oxaziazone, kink mouth rack, Romazon, Surco preparative Rio down, Shinmechiri down, Jichiopiru, Pirazore DOO, Piride DOO, Furupokisamu, base down evening Zon, Benfuruse one preparative, further cell Tokishijimu, like Kisanjion herbicides to cyclo such tralkoxydim. Also, a combination of these Vegetable oils and oil concentrates can also be added to the present invention.

 Next, the compound of the present invention will be described in more detail with reference to examples.

Example 1

 3-[2 — Methyl _ 3 — (3 — Methylisoxazolyl 5 — yl) 1-4-methylsulfonyl] benzoyl 6, 6 — dimethylbiperidine — 2, 4 — dione (Compound No. III 1 2 ) Manufacturing of

2 —Methyl-3 — (3 —Methylisoxazolyl— 5 —yl) — 4-Methylsulfonylbenzoyl chloride 0.85 g of a solution of 30 ml of acetonitrile in room temperature was cooled to room temperature. Then, 6,42-dimethylbiperidine-124-dione (0.42 g) and triethylamine (0.35 g) were added dropwise to a solution of acetonitrile (1 O ml). After reacting at room temperature for 2 hours, 0.75 ml of triethylamine was added to the reaction solution, and then 0.25 ml of acetontocyanhydrin was added, followed by reaction at room temperature for 12 hours. The reaction solution was filtered, the filtrate was concentrated, the residue was dissolved in ethyl acetate, washed with aqueous hydrochloric acid, water and saturated brine, and the organic layer was dried over anhydrous magnesium sulfate. The organic layer was filtered, the solvent was concentrated, methanol was added, and the precipitated crystals were filtered to obtain 0.47 g of the title compound. m.p.258 ° C (decomposition) Table 3 shows the compounds of the present invention including the above Examples.

 Table 4 shows the NMR data of the synthesized compounds in Table 3.

Note: In the physical property values column, [] indicates the melting point (in), and * indicates that there is NMR data (Table 4 below). (Continued) Compound R ¹ R ² R ³ n R ⁶ R ⁷ R ⁸ Z Physical property number

m-i7 CH ₃ S0 ₂ CH ₃ n = 0 CH ₃ CH ₃ H Ph-4-Cl * NMR-9 m-i8 CI S0 ₂ CH ₃ n = 0 CH ₃ CH ₃ H Ph * NMR-10

Π-19 CI S0 ₂ CH ₃ n = 0 CH ₃ CH ₃ HCC 215 ° C dec

Π-20 CI S0 ₂ CH ₃ n = 0 CH ₃ CH ₃ H CH = CH ₂ 204 ° C dec m-2ΐ CI S0 ₂ CH ₃ n = 0 CH ₃ CH ₃ H 3) 2 * NMR-11

Π-22 CI S0 ₂ CH ₃ n = 0 CH ₃ CH ₃ HP 226 ° C dec

IE-23 CH ₃ S0 ₂ CH ₃ n = 0 C2H5 C2 H5 HC * Thigh-12

Π-24 CH ₃ S0 ₂ CH ₃ n = 0 CH ₃ C2H5 HC 220 ° C dec

1-25 CH ₃ SO2 CH3 n = 0 CH ₃ CH ₃ HA * Thigh-13

1-26 CI SO2 CH3 5-CH3 H CH ₃ HC [300]

Π-27 CI S0 ₂ CH ₃ 5-CH3 CH ₃ CH3 HC [219-222]

Π-28 CH ₃ S0 ₂ CH ₃ 5-CHs H CH ₃ HC [205]

IE- 29 CI CI n = 0 CH ₃ CH ₃ HC * MR-14

Π-30 CH ₃ SCH ₃ 5- CI CH ₃ CH ₃ HC [266-272]

Π-31 CH ₃ S0 ₂ CH ₃ 5-C1 CH ₃ CH ₃ HC [281-283]-32 CH ₃ CI 5- CI CH ₃ CH ₃ HC * Thigh-15

Π-33 CH ₃ S0 ₂ CH ₃ n = 0 CH ₃ CH ₃ HL * Thigh-16

Π-34 CH ₃ SO2CH3 n = 0 CH ₃ CH ₃ HM [277-279]

Π-35 CI CI n = 0 CH ₃ CH ₃ HP [102-108] m-36 CI CI n = 0 CH ₃ CH ₃ CH ₃ P [164-165]

Μ-37 CH ₃ SO2 CH3 n = 0 CH ₃ CH ₃ HP [284-288]

ΙΠ-38 CI S0 ₂ CH ₃ n = 0 CH ₃ CH ₃ H 0 [221]

Π-39 CH ₃ S0 ₂ CH ₃ n = 0 CH ₃ CH ₃ HR * Thigh-17

1Π-40 CI SO2 CH3 n = 0 CH ₃ CH ₃ H OC2H4OCH3 [158-159] Table 4

Compound i mm m

 Θ Θ g article number Ή-NMR (5 p p m

 Say d?

Solvent Bok NMR-4 is, <5 ₆ -DMSO, others, CDC1 _3.

ΙΠ-1 1 1.4 (d, 6H), 2.4 (s, 3H), 2.5 (s, 2H), 3.1 (s, 3H), 3.2 (s, 3H), NMR-1 6.5 (s, lH), 7.5 (d, lH), 8.2 (d, 1H)

 1-2 1.4 (s, 6H), 2.l (s, 3H), 2.4 (s, 3H), 2.5 (d, 2H), 3.0 (s, 3H), crash-2 6.4 (s, lH ), 7.4 (d, 2H), 8. l (d, 2H)

 1.35 (s, 3H), 1.4 (s, 3H), 2.0 (s, 3H), 2.4 (s, 3H), 2.5 (d, 2H), 2. T (s, 3H), 3.0 ( s, 3H), 3.1 (s, 3H), 6.2 (s, 1H), 7.2 (s, 1H)

1.4 (s, 6H), 2.1 (s, 3H), 2.4 (s, 2H), 3.2 (s, 3H), 3.3 (m, 2H), 4.4 (m, 2H), 7.5 (d, lH), 7.9 (d, 1H)

 n-io 1.4 (s, 6H), 2.5 (s, 2H), 3.1 (s, 3H), 3.3 (s, 3H), 3.5 (s, 3H), thigh-53.8 (t, 2H) ), 4.4 (t, 2H), 7.l (d, 1H), 8.1 (d, 1H)

 1.4 (s, 6H), 2.5 (s, 2H), 3.1 (s, 3H), 3.2 (S, 3H), 3.51 (s, 3H), 3.52 (s, 3H), 6. 3 (s, 1H), 7.3 (d, 1H), 8.2 (d, 1H)

1.3 On '6H), 2.4 (s, 2H), 3.2 (s, 3H), 3.5 (S, 3H), 3.55 (s, 3H), 6.3 (s, 1H), 6.4 (s, 1H), 7.3 ( d, 1H), 8.2 (d, 1H)

1-16 1.4 (m, 6H), 1.9 (s, 3H), 2.5 (d, 2H), 2.6 (S, 3H), 6.0 (s, 1H), thigh-8 7.2-7.5 (m, 6H), 8. 1 (d, 1H)

 Π-17 1.4 (m, 6H), 1.9 (s, 3H), 2.5 (d, 2H), 2.7 (S, 3H), 5.9 (s, 1H), NMR-9 7.2-7.5 (m, 5H ), 8. l (d, 1H)

 m-i8 1.4 (m, 6H), 2.5 (s, 2H), 2.7 (s, 3H), 5.9 (S, 1H),

 NMR-10 7.2-7.5 (m, 6H), 8.2 (d, 1H)

 m-21 1.4 (m, 6H), 2.5 (s, 2H), 2.9 (m, 6H), 3.3 (S, 3H), 6.0 (s, 1H), thigh-117.3 (d, lH ), 8.0 (d, 1H)

 0.9 (m, 6H), 1.6 (m, 4H), 2.1 (s, 3H), 2.4 (S, 3H), 2.5 (d, 2H), 3.0 (s, 1H), 6.0 (s, 1H) , 6.4 (s, 1H), 7.4 (d, 1H), 8.l (d, 1H)

Π-25 1.2 (s, 6H), 2.l (s, 3H), 2.5 (d, 2H), 2.9 (s, 3H), 6.0 (s, 1H), Thigh-13 7.3 (s, 1H), 7.4 (d, 1H), 8.1 (s, 1H), 8.2 (d, 1H)

 m-29 1.4 (s, 6H), 2. (s, 3H), 2.5 (s, 2H), 6.0 (s, 1H), 6.3 (s, 1H), NMR-14 7.3 (d, lH), 7 . 5 (d, 1H)

 Π-32 1.4 (s, 6H), 2.1 (s, 3H), 2.4 (s, 3H), 2.5 (s, 2H), 5.9 (s, 1H), NMR-15 6.3 (s, lH) ), 7.4 (s, 1H)

 IK-33 1.4 (s, 6H), 2.0 (s, 3H), 2.5 (s, 2H), 3.25 (s, 3H), 4.5 (s, 3H) Thigh-16 5.9 (s, lH), T.5 (d, lH), 8.1 (d, 1H)

IE-39 1.4 (s, 6H), 1.95 (s, 3H), 2.5 (d, 2H), 2.7 (s, 3H), 5.9 (s, 1H) 舰 -17 7.4-8.7 (m, 6H) (Herbicide)

 Next, some formulation examples of the herbicide of the present invention are shown. However, the active ingredient compounds, additives, and the addition ratio can be changed in a wide range without being limited to only this example.

. Parts in Formulation Examples are parts by weight.

Example 2 wettable powder

 Compound of the present invention 20 parts

 White carbon 20 parts

 Diatomaceous earth 5 2 parts

 Sodium alkyl sulfate 8 parts

 The above components were uniformly mixed and finely pulverized to obtain a wettable powder containing 20% of the active ingredient.

Example 3 Emulsion

 Compound of the present invention 20 parts

 Xylene 5 5 parts

 Dimethylformamide 15 parts

 Polyoxyethylene phenyl ether 10 parts

 The above ingredients were mixed and dissolved to obtain an emulsion containing 20% of the active ingredient.

Example 4 granules

 5 parts of the compound of the present invention

 Talc 40 parts

 Cray 3 8 copies

 Bentonite 10

 Sodium alkyl sulfate 7 parts

The above mixture was uniformly mixed and finely ground, and then granulated into granules having a diameter of 0.5 to 1.0 mm to obtain granules having an active ingredient of 5%. The compound of the present invention shows a high herbicidal activity under any conditions of upland crops, in any of soil treatment and foliage treatment, and shows high efficacy against various kinds of upland weeds such as ichibi, inubu, akinoenokorogosa, and wild oats. Also, corn, wheat, barley and other barley, soybeans, potatoes and other crop-selective compounds are also included. In addition, the compound of the present invention also includes a compound having a plant growth regulating effect, such as for producing growth suppression, on useful plants such as crops, ornamental plants, and fruit trees.

 In addition, the compound of the present invention has excellent herbicidal activity against paddy weeds such as Nobie, Tamagayari, Omodaka and Hotaru, and has selectivity for rice.

 Furthermore, the compound of the present invention can be applied to the control of weeds in orchards, lawns, track ends, vacant lots and the like.

 The compounds of the present invention also include those having fungicidal activity, insecticidal and acaricidal activity. Next, test examples relating to the effect of the herbicide of the present invention will be shown.

 The herbicidal effect was investigated according to the following criteria and expressed as a herbicidal index. Survey criteria

 Killing grass killing grass

 0% 0

 20 to 29% 2

 40 to 49% 4

 6 0-6 9% 6

 8 0-8 9% 8

 1 0 0% 1 0

 The numbers 1, 3, and 5.9 are 0 and 2, 2 and 4, 4 and 6, 6 and 8, respectively.

Indicates a value between 8 and 10.

(Aboveground fresh grass weight in untreated area-Above ground fresh grass weight in treated area) Herbicidal rate (%) 100 0 Aboveground fresh grass weight in untreated area

2 0 0 cm to Takashi塡the soil in pots of ^2, Ichibi to the surface, I j views, seeded Onamomi, Akinoeno Korogusa, the each seed of corn, lightly growth of in the soil covering after a greenhouse I let you. When each plant has grown to a height of 5 to 25 cm, 100 liters / ha of a water dilution of the emulsion shown in Example 3 is applied so that the active ingredient has a predetermined dose. A large amount was sprayed on the foliage with a small sprayer. Three weeks later, the phytotoxicity of the crop and the herbicidal effect of the weeds were investigated in accordance with the above-mentioned survey criteria.

 Table 5

産業上の利用可能性 ：

Industrial applicability:

 The compound of the present invention can be industrially advantageously synthesized, is suitable as a herbicide for controlling weeds such as corn, and is industrially useful.

Claims

The scope of the claims  'General formula (1)

[Wherein, R ¹ and R ² each independently represent a nitrogen atom, a cyano group, a halogen atom , C alkyl group, alkoxy group, C _i-6 haloalkyl group, C _i-6 Al Kiruchio group, an alkyl sulfide alkylsulfonyl group or a C - represents a ₆ alkylsulfonyl group!. R ³ is a nitro group, Shiano group, a halogen atom, - ₆ alkyl group, alkoxy group, C -! Haloalkyl group, C, - ₆ alkylthio groups, C _i-S alkylsulfinyl Finiru group or a C alkylsulfonyl Represents a group.  n represents 0, 1, and 2. R ⁴ and R ⁵ each independently represent a hydrogen atom, a halogen atom, a d-alkyl group, a d-haloalkyl group, an alkoxyalkyl group, an alkylcarbonyloxy C ぃ₆ alkyl group, or a hydroxyalkyl group; , R ⁴ and R ⁵ may be taken together to form an alkylene chain having 2 to 5 carbon atoms R ⁶ is a hydrogen atom, C - represents an _alkyl group, human Dorokishi _d-6 alkyl group, d haloalkyl group!. However, when R ⁶ is a hydrogen atom, n is not 0. R ⁷ represents a d-alkyl group, a hydroxy C i alkyl group, or a C i- ₆ haloalkyl group; and R ⁶ and R ⁷ together form an alkylene chain having 2 to 5 carbon atoms. R ⁷ may combine with R ⁵ to form a bond or an alkylene chain having 1 to 4 carbon atoms. R ⁸ is a hydrogen atom, _d-beta alkyl groups, C ₂ - _e alkenyl groups, C ₂ - ₆ Arukini le groups, C l-haloalkyl groups, C ₂ - haloalkenyl groups, C ₂ - ₆ haloalkynyl groups, C alkoxy groups, C ₂ - _beta Arukeniruokishi groups, C ₂ - _e Arukiniruokishi It represents the _e Haroaru Kiniruokishi group - group, haloalkoxy group, C ₂ - ₆ haloalkenyloxy O alkoxy group, c _2. Z is formyl group, Moruhori amino group, an alkoxy group, d-6 alkoxy C 1 -6 alkoxy, C ₂ - 6 alkenyl group, an alkoxycarbonyl group, a di C 1 -6 alkoxymethyl group, _di-6 alkylthiomethyl group , An optionally substituted amino group, an optionally substituted phenyl group, an optionally substituted heterocyclic group or a formula — C (R ⁹ ) —NR ¹⁰ (where R ⁹ is a hydrogen atom or d - an _e alkyl group, R ¹⁰ is, human Dorokishi group, alkyl group, C -! ₆ haloalkyl group, C ₂ - ₆ alkenyl le group, C ₂ _ _e haloalkenyl, C ₂ - ₆ alkynyl group, C ₂ - ₆ haloalkynyl group , C 3 -8 cycloalkyl group, C _i-6 alkoxy group, alkoxy C i-4 Al kill group, haloalkoxy group, C ₃ - 8 cycloalkyl O alkoxy group, C 2 -8 Al Keniruokishi groups, C 2 - 6 haloalkenyl O alkoxy group, C ₂ - ₆ Arukiniruokishi groups, C ₂ - ₆ C port Arukiniruokishi group, an optionally substituted amino group, an optionally substituted Fuweniru group, optionally substituted Yoibe Represents an benzyl group, an optionally substituted phenyloxy group or an optionally substituted benzyloxy group. ) Represents a group represented by ] Or a salt thereof.  2. In the definition of Z in claim 1, the optionally substituted heterocyclic group is any of the following groups R ¹

(Wherein, R ¹¹ and R ¹² are each independently a hydrogen atom, a halogen atom, d- 6 represents an alkyl group or an alkoxy group. 2. The derivative or salt thereof according to item 1, which is selected from the group consisting of:  3. General formula (1)

(Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ^e , R ⁷ , R ⁸ , n, and Z have the same meanings as in claim 1). A herbicide characterized by containing one or more of a gindione derivative or a salt thereof as an active ingredient. 4. General formula (Γ)

(Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ , η and Ζ have the same meanings as in claim 1) or a substituted pyridindione derivative represented by the following formula: A herbicide comprising one or more of its salts as an active ingredient.  5. General formula (1 ")

(Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ and Ζ have the same meanings as in claim 1) or a salt thereof. A herbicide comprising one or more of the following as an active ingredient.