JP2007001944A - 3,4-dihydro-1,3'-biquinoline-2-one derivative - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound useful as an active ingredient of an agrochemical having excellent germicidal activities against various kinds of plant diseases, and capable of controlling blast or the like with a small amount of the chemical. <P>SOLUTION: The agrochemical contains a compound represented by the general formula (wherein, Ra, Rb, Rc and Rd are each a hydrogen atom, a halogen atom, a hydroxide group, a 1-6C alkyl group, a 2-6C alkenyl group, a 2-6C alkynyl group, a 1-6C alkoxy group, an acyl group, a carboxy group, a cyano group, an acyloxy group, an aryl group or an aralkyl group; X is a halogen atom, a 1-6C alkyl group, a 2-6C alkenyl group, a 2-6C alkynyl group, a 1-6C alkoxy group, a 1-6C alkylthio group, a 1-6C alkylsulfinyl group, a 1-6C alkylsulfonyl group, an aryl group, a heteroaryl group, an amino group, an acyl group, a carboxy group, an acyloxy group or a cyano group; Y is a substituent selected from the group consisting of a halogen atom, a 1-6C alkyl group, a 1-6C alkoxy group and a hydroxy group; m is an integer of 0-4; and n is an integer of 0-6) in the figure, or a salt thereof as an active ingredient. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a 3,4-dihydro-1,3'-biquinolin-2-one derivative or a salt thereof, and an agrochemical containing the same as an active ingredient.

  A compound in which the piperidine ring is substituted at the 1-position of the dihydroquinolinone ring as an analog of Nociceptin in WO 2002/85291, and as a compound having vasopressin antagonistic activity in JP-A-6 / 135959 Although described, a compound in which the quinoline ring is substituted at the 1-position of the dihydroquinolinone ring at the 3-position is not described, and there is no description about the agricultural and horticultural fungicides. In addition, JP 2002/509928 A discloses a compound in which a heterocycle is bonded to the 1-position of a dihydroquinolinone ring mainly through an alkylene chain as a serine protease inhibitor, but the quinoline ring is directly in the 3-position. The bound compound is not described, and there is no description about the agricultural and horticultural fungicide. Thus, it has not been known that a compound in which the quinoline ring is directly bonded to the 1-position of the dihydroquinolinone ring at the 3-position can be used as an agricultural and horticultural fungicide.

As a result of extensive research on the dihydroquinolinone derivative, the present inventors have found that a 3,4-dihydro-1,3′-biquinolin-2-one derivative in which a quinoline is bonded to the 1-position of the dihydroquinolinone ring at the 3-position. However, rice blast that has excellent bactericidal activity against various plant diseases and is useful as an active ingredient of agricultural chemicals, and particularly causes serious damage to agricultural and horticultural crops among plant fungi (Magnaporthe grisea) and tomato, cucumber, and green beans (Botrytis cinerea) have been found to be controllable at a low dose, and the present invention has been completed.
International Publication No. 2002/85291 Pamphlet JP-A-6-135959 Japanese translation of PCT publication No. 2002-509928

式中、
Ｒａ、Ｒｂ、Ｒｃ及びＲｄは、同一、若しくは異なっていてもよく、
水素原子；ハロゲン原子；水酸基；Ｃ₁〜Ｃ₆アルコキシ基；アシル基；カルボキシル基；シアノ基；アシルオキシ基；ハロゲン原子、水酸基、Ｃ₁〜Ｃ₆アルコキシ基、Ｃ₁〜Ｃ₆アルキルチオ基、Ｃ₁〜Ｃ₆アルキルスルフィニル基、Ｃ₁〜Ｃ₆アルキルスルホニル基及びフェノキシ基からなる群から選ばれる同一若しくは異なった１〜３個の置換基で置換されてよいＣ₁〜Ｃ₆アルキル基；ハロゲン原子、水酸基、Ｃ₁〜Ｃ₆アルコキシ基、Ｃ₁〜Ｃ₆アルキルチオ基、Ｃ₁〜Ｃ₆アルキルスルフィニル基、Ｃ₁〜Ｃ₆アルキルスルホニル基、フェニル基及びフェノキシ基からなる群から選ばれる同一若しくは異なった１〜３個の置換基で置換されてよいＣ₂〜Ｃ₆アルケニル基；ハロゲン原子、水酸基、Ｃ₁〜Ｃ₆アルコキシ基、Ｃ₁〜Ｃ₆アルキルチオ基、Ｃ₁〜Ｃ₆アルキルスルフィニル基、Ｃ₁〜Ｃ₆アルキルスルホニル基、フェニル基及びフェノキシ基からなる群から選ばれる同一若しくは異なった１〜３個の置換基で置換されてよいＣ₂〜Ｃ₆アルキニル基；ハロゲン原子、同一若しくは異なった１〜３個のハロゲン原子で置換されてよいＣ₁〜Ｃ₆アルキル基、Ｃ₁〜Ｃ₆アルコキシ基、ニトロ基、シアノ基、水酸基及び同一若しくは異なった１〜２個のＣ₁〜Ｃ₆アルキル基又はアシル基で置換されてよいアミノ基からなる群から選ばれる同一若しくは異なった１〜５個の置換基で置換されてよいアリール基；ハロゲン原子、同一若しくは異なった１〜３個のハロゲン原子で置換されてよいＣ₁〜Ｃ₆アルキル基、Ｃ₁〜Ｃ₆アルコキシ基、ニトロ基、シアノ基、水酸基及び同一若しくは異なった１〜２個のＣ₁〜Ｃ₆アルキル基又はアシル基で置換されてよいアミノ基からなる群から選ばれる同一若しくは異なった１〜６個の置換基で置換されてよいアラルキル基であるか、又は、
ＲaとＲb、ＲcとＲdあるいはＲbとＲcが結合する炭素原子あるいはアルキレンと一緒になって形成する、ハロゲン原子、Ｃ₁〜Ｃ₆アルキル基、Ｃ₁〜Ｃ₆アルコキシ基及びフェノキシ基からなる群から選ばれる同一若しくは異なった１〜３個の置換基で置換されてよいＣ₃〜Ｃ₁₀シクロアルキル環を表し、
Ｘは、同一又は異なっていてもよく、
ハロゲン原子；水酸基；Ｃ₁〜Ｃ₆アルコキシ基；アシル基；カルボキシル基；シアノ基；アシルオキシ基；ニトロ基；Ｃ₁〜Ｃ₆アルキルチオ基；Ｃ₁〜Ｃ₆アルキルスルフィニル基；Ｃ₁〜Ｃ₆アルキルスルホニル基；ハロゲン原子、水酸基、Ｃ₁〜Ｃ₆アルコキシ基、Ｃ₁〜Ｃ₆アルキルチオ基、Ｃ₁〜Ｃ₆アルキルスルフィニル基、Ｃ₁〜Ｃ₆アルキルスルホニル基及びフェノキシ基からなる群から選ばれる同一若しくは異なった１〜３個の置換基で置換されてよいＣ₁〜Ｃ₆アルキル基；ハロゲン原子、水酸基、Ｃ₁〜Ｃ₆アルコキシ基、Ｃ₁〜Ｃ₆アルキルチオ基、Ｃ₁〜Ｃ₆アルキルスルフィニル基、Ｃ₁〜Ｃ₆アルキルスルホニル基、フェニル基及びフェノキシ基からなる群から選ばれる同一若しくは異なった１〜３個の置換基で置換されてよいＣ₂〜Ｃ₆アルケニル基；ハロゲン原子、水酸基、Ｃ₁〜Ｃ₆アルコキシ基、Ｃ₁〜Ｃ₆アルキルチオ基、Ｃ₁〜Ｃ₆アルキルスルフィニル基、Ｃ₁〜Ｃ₆アルキルスルホニル基、フェニル基及びフェノキシ基からなる群から選ばれる同一若しくは異なった１〜３個の置換基で置換されてよいＣ₂〜Ｃ₆アルキニル基；ハロゲン原子、同一若しくは異なった１〜３個のハロゲン原子で置換されてよいＣ₁〜Ｃ₆アルキル基、Ｃ₁〜Ｃ₆アルコキシ基、ニトロ基、シアノ基、水酸基及び同一若しくは異なった１〜２個のＣ₁〜Ｃ₆アルキル基又はアシル基で置換されてよいアミノ基からなる群から選ばれる同一若しくは異なった１〜５個の置換基で置換されてよいアリール基；ハロゲン原子、同一若しくは異なった１〜３個のハロゲン原子で置換されてよいＣ₁〜Ｃ₆アルキル基及びＣ₁〜Ｃ₆アルコキシ基からなる群から選ばれる同一若しくは異なった１〜６個の置換基で置換されてよいヘテロアリール基；同一若しくは異なった１〜２個のＣ₁〜Ｃ₆アルキル基若しくはアシル基で置換されてよいアミノ基を表し、
Ｙは、同一、もしくは異なっていてもよく、ハロゲン原子、Ｃ₁〜Ｃ₆アルキル基、Ｃ₁〜Ｃ₆アルコキシ基及び水酸基からなる群から選ばれる置換基を表し、
ｍは、０〜４の整数を表し、
ｎは、０〜６の整数を表す、
で表される化合物又はその塩である。 The present invention provides a general formula

Where
Ra, Rb, Rc and Rd may be the same or different,
Hydrogen atom; halogen atom; hydroxyl group; C ₁ -C ₆ alkoxy group; acyl group; carboxyl group; cyano group; acyloxy group; halogen atom, hydroxyl group, C ₁ -C ₆ alkoxy group, C ₁ -C ₆ alkylthio group, C ₁ -C ₆ alkylsulfinyl group, C ₁ -C ₆ alkylsulfonyl group and the same or different 1-3 and which may be C ₁ -C ₆ alkyl group substituted with a substituent selected from the group consisting of a phenoxy group; a halogen atom, the same selected hydroxyl, C ₁ -C ₆ alkoxy group, C ₁ -C ₆ alkylthio group, C ₁ -C ₆ alkylsulfinyl groups, C ₁ -C ₆ alkylsulfonyl group, from the group consisting of phenyl and phenoxy groups or different 1-3 may be substituted with a substituent C ₂ -C ₆ alkenyl group; a halogen atom, a hydroxyl group, C ₁ -C ₆ alkoxy group, C ₁ -C ₆ Alkylthio group, C ₁ -C ₆ alkylsulfinyl group, C ₁ -C ₆ alkylsulfonyl group, or C ₂ to be substituted by the same or different 1 to 3 substituents selected from the group consisting of phenyl and phenoxy groups -C ₆ alkynyl group; a halogen atom, the same or different 1 to 3 may C ₁ -C ₆ alkyl group substituted by a halogen atom, C ₁ -C ₆ alkoxy group, a nitro group, a cyano group, a hydroxyl group, and the same Or an aryl group which may be substituted with the same or different 1 to 5 substituents selected from the group consisting of different 1 to 2 C ₁ -C ₆ alkyl groups or an amino group which may be substituted with an acyl group; halogen atoms, the same or different 1-3 is substituted with a halogen atom or C ₁ -C ₆ alkyl group, C ₁ -C ₆ alkoxy group, a nitro group, a cyano group, a hydroxyl group及Same or different one to two C ₁ -C ₆ alkyl group or the same or different 1 to 6 substituted with a substituent which may be aralkyl group selected from the group consisting of amino group which may be substituted with an acyl group Or
A group consisting of a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group, and a phenoxy group, which are formed together with carbon atoms or alkylenes to which R a and R b, R c and R d or R b and R c are bonded. represent the same or different and may be substituted with 1-3 substituents C ₃ -C ₁₀ cycloalkyl ring selected from,
X may be the same or different;
A halogen atom; a hydroxyl group; C ₁ -C ₆ alkoxy group; an acyl group; a carboxyl group; a cyano group; an acyloxy group; nitro group; C ₁ -C ₆ alkylthio group; C ₁ -C ₆ alkylsulfinyl group; C ₁ -C ₆ an alkylsulfonyl group; a halogen atom, a hydroxyl group, C ₁ -C ₆ alkoxy group, selected from C ₁ -C ₆ alkylthio group, C ₁ -C ₆ alkylsulfinyl group, the group consisting of C ₁ -C ₆ alkylsulfonyl group and a phenoxy group C ₁ -C ₆ alkyl group which may be substituted with the same or different 1 to 3 substituents; halogen atom, hydroxyl group, C ₁ -C ₆ alkoxy group, C ₁ -C ₆ alkylthio group, C ₁ -C ₆ alkylsulfinyl group, still at C ₁ -C ₆ alkylsulfonyl group, the same or different 1 to 3 substituents selected from the group consisting of phenyl and phenoxy groups And which may be C ₂ -C ₆ alkenyl group; a halogen atom, a hydroxyl group, C ₁ -C ₆ alkoxy group, C ₁ -C ₆ alkylthio group, C ₁ -C ₆ alkylsulfinyl group, C ₁ -C ₆ alkylsulfonyl group, same or different 1-3 is substituted with a substituent which may C ₂ to -C ₆ alkynyl group selected from the group consisting of phenyl group and a phenoxy group; a halogen atom, the same or different 1 to 3 halogen atoms which may be substituted C ₁ -C ₆ alkyl group, C ₁ -C ₆ alkoxy group, a nitro group, a cyano group, a hydroxyl group and the same or different one to two C ₁ -C ₆ alkyl group or an acyl group An aryl group which may be substituted with the same or different 1 to 5 substituents selected from the group consisting of optionally amino groups; a halogen atom, the same or different 1 to 3 halogen atoms In which may be substituted C ₁ -C ₆ alkyl and C ₁ -C ₆ same or different 1-6 is substituted with a substituent which may heteroaryl group selected from the group consisting of an alkoxy group; the same or different represents one to two C ₁ -C ₆ alkyl group or amino group which may be substituted with an acyl group,
Y are identical or may be different, represents a halogen atom, C ₁ -C ₆ alkyl group, a substituent selected from the group consisting of C ₁ -C ₆ alkoxy group and a hydroxyl group,
m represents an integer of 0 to 4,
n represents an integer of 0 to 6,
Or a salt thereof.

  In the present invention, the “halogen atom” is a fluorine atom, chlorine atom, bromine atom or iodine atom, preferably a fluorine atom, chlorine atom or bromine atom, more preferably a fluorine atom or chlorine atom. And most preferably a fluorine atom.

In the present invention, “C ₁ -C ₆ alkyl group” means, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, isopentyl group. 2-methylbutyl group, neopentyl group, 1-ethylpropyl group, hexyl group, 4-methylpentyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 3,3-dimethylbutyl group , 2,2-dimethylbutyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 2-ethylbutyl group A linear or branched alkyl group having 1 to 6 carbon atoms, preferably a linear or branched alkyl group having 1 to 5 carbon atoms (C ₁ -C ₅ alkyl group), and more preferably The carbon A linear or branched alkyl group having ₁ to ₄ carbon atoms (C ₁ -C ₄ alkyl group), and even more preferably a linear or branched alkyl group having 1 to 3 carbon atoms (C ₁ a -C ₃ alkyl group), particularly preferably a methyl group, an ethyl group or propyl group, most preferably a methyl group or an ethyl group.

In the present invention, the “C ₃ -C ₁₀ cycloalkyl group” is, for example, a monocyclic group having 3 to 10 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, or a norbornyl group. It is a bicyclic cycloalkyl group, and preferably a cyclopentyl group, a cyclohexyl group or a cycloheptyl group.

In the present invention, the “C ₂ -C ₆ alkenyl group” may be either linear or branched, and may contain any number of one or more double bonds. For example, vinyl group, prop-1-en-1-yl group, allyl group, isopropenyl group, but-1-en-1-yl group, but-2-en-1-yl group, but-3-ene -1-yl group, 2-methylprop-2-en-1-yl group, 1-methylprop-2-en-1-yl group, penta-1-en-1-yl group, penta-2-ene-1 -Yl group, penta-3-en-1-yl group, penta-4-en-1-yl group, 3-methylbut-2-en-1-yl group, 3-methylbut-3-en-1-yl Group, hexa-1-en-1-yl group, hexa-2-en-1-yl group, hexa-3-en-1-yl group, hexa-4-en-1-yl group, hexa-5- Examples thereof include an en-1-yl group and a 4-methylpent-3-en-1-yl group.

In the present invention, the “C ₂ -C ₆ alkynyl group” may be linear or branched, and may contain any number of one or more triple bonds. For example, ethynyl group, prop-1-in-1-yl group, prop-2-yn-1-yl group, but-1-in-1-yl group, but-3-in-1-yl group, -Methylprop-2-yn-1-yl group, penta-1-in-1-yl group, penta-4-in-1-yl group, hexa-1-in-1-yl group, hexa-5-in A -1-yl group etc. can be illustrated.

In the present invention, the “C ₁ -C ₆ alkoxy group” means, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, an s-butoxy group, a t-butoxy group, a pentyloxy group, Isopentyloxy group, 2-methylbutoxy group, neopentyloxy group, 1-ethylpropoxy group, hexyloxy group, (4-methylpentyl) oxy group, (3-methylpentyl) oxy group, (2-methylpentyl) Oxy group, (1-methylpentyl) oxy group, 3,3-dimethylbutoxy group, 2,2-dimethylbutoxy group, 1,1-dimethylbutoxy group, 1,2-dimethylbutoxy group, 1,3-dimethylbutoxy group A straight-chain or branched alkoxy group having 1 to 6 carbon atoms such as a group, 2,3-dimethylbutoxy group, 2-ethylbutoxy group , Preferably a straight or branched alkoxy group having 1 to 4 carbon atoms (C ₁ -C ₄ alkoxy group), more preferably a methoxy group, an ethoxy group or isopropoxy group, more More preferably a methoxy group or an ethoxy group, and most preferably a methoxy group.

In the present invention, the “C ₁ -C ₆ alkylthio group” means, for example, methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isopentylthio group, neopentylthio group, 3,3-dimethylbutylthio group. , A straight-chain or branched alkylthio group having 1 to 6 carbon atoms such as 2-ethylbutylthio group, preferably a straight-chain or branched alkylthio group having 1 to 4 carbon atoms, More preferably, it is a methylthio group.

In the present invention, “C ₁ -C ₆ alkylsulfinyl group” means, for example, methylsulfinyl group, ethylsulfinyl group, propylsulfinyl group, isopropylsulfinyl group, butylsulfinyl group, isopentylsulfinyl group, neopentylsulfinyl group, 3 , 3-dimethylbutylsulfinyl group, 2-ethylbutylsulfinyl group or the like, which is a straight chain or branched alkylsulfinyl group having 1 to 6 carbon atoms, preferably a straight chain having 1 to 4 carbon atoms or It is a branched alkylsulfinyl group, more preferably a methylsulfinyl group.

In the present invention, the “C ₁ -C ₆ alkylsulfonyl group” means, for example, a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, an isopentylsulfonyl group, a neopentylsulfonyl group, 3 , 3-dimethylbutylsulfonyl group, a straight-chain or branched alkylsulfonyl group having 1 to 6 carbon atoms such as a 2-ethylbutylsulfonyl group, A branched alkylsulfonyl group, and more preferably a methylsulfonyl group.

  In the present invention, examples of the “aryl group” include phenyl group, 1-naphthyl group, 2-naphthyl group, anthracenyl group, phenanthrenyl group, acenaphthylenyl group and the like.

  In the present invention, the “heteroaryl group” may be monocyclic or polycyclic, and a heteroaryl group containing one or two or more of the same or different ring-constituting heteroatoms can be used. . Although the kind of hetero atom is not specifically limited, For example, a nitrogen atom, an oxygen atom, a sulfur atom etc. can be illustrated. Examples of heteroaryl groups include furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, dihydroisoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, thiadiazolyl, triazolyl , Tetrazolyl group, pyridyl group, azepinyl group, oxazepinyl group and the like, 5-7 membered monocyclic heteroaryl group. The polycyclic heteroaryl group constituting the heteroarylalkyl group includes benzofuranyl group, isobenzofuranyl group, benzothienyl group, indolyl group, isoindolyl group, indazolyl group, benzoxazolyl group, benzoisoxazolyl group , Benzothiazolyl, benzoisothiazolyl, benzoxiadiazolyl, benzothiadiazolyl, benzotriazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl 8-14 members such as a group, pteridinyl group, carbazolyl group, carbolinyl group, acridinyl group, 2-acridinyl, 3-acridinyl, 4-acridinyl, 9-acridinyl, phenoxazinyl group, phenothiazinyl group, phenazinyl group Polycyclic heteroaryl groups.

In the present invention, examples of the “aralkyl group” include a group in which one or two or more hydrogen atoms of the “C ₁ -C ₆ alkyl group” are substituted with the “aryl group”. For example, benzyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, anthracenylmethyl group, phenanthrenylmethyl group, acenaphthylenylmethyl group, diphenylmethyl group, 1-phenethyl group, 2-phenethyl group 1- (1-naphthyl) ethyl group, 1- (2-naphthyl) ethyl group, 2- (1-naphthyl) ethyl group, 2- (2-naphthyl) ethyl group, 3-phenylpropyl group, 3- ( 1-naphthyl) propyl group, 3- (2-naphthyl) propyl group, 4-phenylbutyl group, 4- (1-naphthyl) butyl group, 4- (2-naphthyl) butyl group, 5-phenylpentyl group, 5 Examples include-(1-naphthyl) pentyl group, 5- (2-naphthyl) pentyl group, 6-phenylhexyl group, 6- (1-naphthyl) hexyl group, 6- (2-naphthyl) hexyl and the like. It can be.

In the present invention, the “C ₁ -C ₆ alkyl group which may be substituted with 1 to 3 halogen atoms which are the same or different” includes, for example, trifluoromethyl other than the above “C ₁ -C ₆ alkyl group” Group, trichloromethyl group, difluoromethyl group, dichloromethyl group, dibromomethyl group, fluoromethyl group, chloromethyl group, bromomethyl group, iodomethyl group, 2,2,2-trichloroethyl group, 2,2,2- Trifluoroethyl group, 2-bromoethyl group, 2-chloroethyl group, 2-fluoroethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group, 4-fluorobutyl group, 3-fluoro-2- Same or different 1 to 3 such as methylpropyl group, 3,3,3-trifluoro-2-methylpropyl group, 6,6,6-trichlorohexyl group The “C ₁ -C ₆ alkyl group” substituted by the above-mentioned “halogen atoms”, preferably the above-mentioned “C ₁ -C” optionally substituted by ₁ to 3 of the “halogen atoms”. _{1 to} C ₄ alkyl group ”, more preferably, the above“ C _{1 to} C ₃ alkyl group ”which may be substituted with ₁ to ₃ “ fluorine or chlorine atoms ”which are the same or different, More preferably a methyl group, an ethyl group, a propyl group, a chloromethyl group or a trifluoromethyl group, and particularly preferably a methyl group, an ethyl group or a trifluoromethyl group.

In the present invention, “amino group which may be substituted with the same or different 1 to 2 C ₁ -C ₆ alkyl groups” means, in addition to the amino group, 1 to 2 of the same or different “C ₁ The “˜C ₆ alkyl group” is an amino group substituted, and examples thereof include a dimethylamino group and a diethylamino group.

In the present invention, the “acyl group” is, for example, a formyl group, a carbonyl group to which the “C ₁ -C ₆ alkyl group” is bonded (C ₂ -C ₇ alkylcarbonyl group), or the “C ₂ -C ₆ alkenyl group”. ”Bonded to a carbonyl group (C _{3 to} C ₇ alkenylcarbonyl group), the above“ aryl group ”bonded to a carbonyl group (“ arylcarbonyl group ”), and the above“ C _{1 to} C ₆ alkoxy group ”bonded to a carbonyl group (C ₂ -C ₇ alkoxycarbonyl group) or the "same or different one to two C ₁ -C ₆ alkyl group which may be substituted amino group" is bonded to carbonyl group (C ₂ -C ₇ alkylamino a carbonyl group), preferably a number from 2 to 5 straight-chain or branched-chain alkyl group carbon (C ₂ -C ₅ alkylcarbonyloxy group), 2-7 pieces of an alkoxycarbonyl atoms Boniru a group (C ₂ -C ₇ alkoxycarbonyl group), more preferably, an acetyl group, a methoxycarbonyl group or an ethoxycarbonyl group.

In the present invention, the “acyloxy group” is, for example, a formyloxy group, a carbonyloxy group (C ₂ -C ₇ alkylcarbonyloxy group) to which the “C ₁ -C ₆ alkyl group” is bonded, or the “C ₂ -C 6”. ₆ alkenyl group "is bonded to carbonyl group (C ₃ -C ₇ alkenylcarbonyl group), the" aryl group "is bonded to carbonyl group (" arylcarbonyl group "), the" C ₁ -C ₆ alkoxy carbonyloxy group-oxy group "is bound (C ₂ -C ₇ alkoxycarbonyloxy group) or the" same or different one to two C ₁ -C ₆ alkyl amino group which may be substituted with group "is bonded carbonyloxy group (aminocarbonyl group, C ₂ -C ₇ alkylaminocarbonyl group, a di (C ₂ -C ₇ alkyl) Aminokaru A Niruokishi group), preferably a number from 2 to 5 straight-chain or branched alkylcarbonyloxy group having a carbon (C ₂ -C ₅ alkylcarbonyloxy group), number 2-7 alkyl aminocarbonyloxy carbon a group (C ₂ -C ₇ alkyl El aminocarbonyl group), more preferably acetoxy.

In the present invention, “from the group consisting of a halogen atom, a hydroxyl group, a C ₁ -C ₆ alkoxy group, a C ₁ -C ₆ alkylthio group, a C ₁ -C ₆ alkylsulfinyl group, a C ₁ -C ₆ alkylsulfonyl group and a phenoxy group. The C ₁ -C ₆ alkyl group which may be substituted with the same or different 1 to 3 substituents selected is the above-mentioned “C ₁ -C ₆ alkyl group” and the above “the same or different 1 to 3 In addition to the “C ₁ -C ₆ alkyl group which may be substituted with a halogen atom”, for example, the above “C ₁ -C ₆ alkyl group”, methoxymethyl group substituted by a hydroxyl group such as a hydroxymethyl group and a hydroxyethyl group , ethoxymethyl group, ethoxyethyl group, propoxy same or different 1 to 3 of the aforementioned "C ₁ -C substituted by" C ₁ -C ₆ alkoxy group "such as a methyl group _The “C ₁ -C ₆ alkyl group” substituted with a phenoxy group such as “ ₆ alkyl group”, phenoxymethyl group, phenoxyethyl group, 2-methoxy-1-chloromethyl group, 3-phenoxy-2-bromo- A group consisting of a halogen atom, the C ₁ -C ₆ alkoxy group, a C ₁ -C ₆ alkylthio group, a C ₁ -C ₆ alkylsulfinyl group, a C ₁ -C ₆ alkylsulfonyl group and a phenoxy group, such as a 2-methoxypropyl group The “C ₁ -C ₆ alkyl group” substituted with two or more substituents selected from

In the present invention, “C ₂ -C ₆ alkenyl group which may be substituted with 1 to 3 identical or different substituents selected from the group consisting of a halogen atom, a C ₁ -C ₆ alkoxy group, a phenyl group and a phenoxy group” Is the above-mentioned “C ₂ -C ₆ alkenyl group” and the above-mentioned “C ₂ substituted with 1 to 3 halogen atoms, which are the same or different, such as 3-chloroallyl group, 4-bromo-2-butenyl group and the like. ˜C ₆ alkenyl group ”, 3-methoxy-2-propenyl group, 4-ethoxy-3-butenyl group and the like substituted with ₁ to 3 of the above“ C ₁ -C ₆ alkoxy group ”. "C ₂ -C ₆ alkenyl group", 1-phenylvinyl group, a styryl group, wherein "C ₂ -C ₆ alkenyl group" which is substituted by a phenyl group such as a cinnamyl group, 3-phenoxy-2-butenyl The substituted phenoxy groups, such as "C ₂ -C ₆ alkenyl group", and such as 4-methoxy-3-chloro-2-butenyl group, a halogen atom, consisting of the C ₁ -C ₆ alkoxy group and phenoxy group The “C ₂ -C ₆ alkenyl group” substituted with two or more substituents selected from the group is also included.

In the present invention, “a C ₂ -C ₆ alkynyl group which may be substituted with 1 to 3 identical or different substituents selected from the group consisting of a halogen atom, a C ₁ -C ₆ alkoxy group and a phenoxy group” In addition to the “C ₂ -C ₆ alkynyl group”, the “C ₂ -C ₆ alkynyl group” and the “C ₂ -C ₆ alkynyl group” substituted with the same or different 1 to 3 halogen atoms such as 3-chloro-2-propynyl group and 4-bromo-2-butynyl group. Substituted with ₁ to 3 above-mentioned “C ₁ -C ₆ alkoxy groups” which are the same or different, such as “ _2- C ₆ alkynyl group”, 3-methoxy-2-propynyl group, 4-ethoxy-3-butynyl group, etc. the "C ₂ -C ₆ alkynyl group", 3-phenoxy-2-a which is substituted by phenoxy groups such as a butynyl group "C ₂ -C ₆ alkynyl group", and 4-methoxy-4-chloro-2-butynyl Base Etc., including a halogen atom, a C ₁ -C ₆ the "C ₂ -C ₆ alkynyl group" which is substituted by two or more substituents selected from alkoxy and the group consisting of a phenoxy group.

In the present invention, “a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group, a nitro group, a cyano group, a hydroxyl group and the same or different, which may be substituted with the same or different 1 to 3 halogen atoms. different 1-2 C ₁ -C ₆ alkyl group or the same or different 1 to 5 substituents may aryl group is substituted with a group selected from the group consisting of amino group which may be substituted with an acyl group "means In addition to the above “aryl group”, the above “aryl group” substituted with 1 to 5 halogen atoms which are the same or different, 1 to 5 “the same or different 1 to 3” which are the same or different The “aryl group” substituted with a “C ₁ -C ₆ alkyl group which may be substituted with a halogen atom”, or the above-mentioned “aryl group” substituted with 1 to 5 “C ₁ -C ₆ alkoxy groups” which are the same or different. “Aryl group”, “aryl group” substituted with 1 to 5 nitro groups, “aryl group” substituted with 1 to 6 cyano groups, and “aryl group” substituted with 1 to 5 hydroxyl groups In addition to the “aryl group”, a halogen atom, the above “C ₁ -C ₆ alkyl group which may be substituted with the same or different 1 to 3 halogen atoms”, the “C ₁ -C ₆ alkoxy group”, a nitro group, The above-mentioned “aryl” substituted with two or more substituents selected from the group consisting of a cyano group, a hydroxyl group and the same or different 1-2 C ₁ -C ₆ alkyl group or an amino group which may be substituted with an acyl group Also includes “group”.

In the present invention, “a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group, a nitro group, a cyano group, a hydroxyl group and the same or different, which may be substituted with the same or different 1 to 3 halogen atoms. “An aralkyl group which may be substituted with the same or different 1 to 6 substituents selected from the group consisting of different 1 to 2 C ₁ -C ₆ alkyl groups or amino groups which may be substituted with acyl groups” In addition to the “aralkyl group”, the “aralkyl group” substituted with 1 to 6 halogen atoms that are the same or different, and 1 to 6 of the same or different that are the same or different it is substituted by the substituted by a halogen atom which may be substituted C ₁ -C ₆ alkyl group "," aralkyl group ", the same or different 1-6 of the" C ₁ -C ₆ alkoxy group " Furthermore, the “aralkyl group” substituted with 1 to 6 nitro groups, the “aralkyl group” substituted with 1 to 6 cyano groups, and substituted with 1 to 6 hydroxyl groups In addition to the “aralkyl group”, a halogen atom, the “C ₁ -C ₆ alkyl group which may be substituted with the same or different 1 to 3 halogen atoms”, the “C ₁ -C ₆ alkoxy group”, Substituted by two or more substituents selected from the group consisting of a nitro group, a cyano group, a hydroxyl group, and an amino group which may be substituted with the same or different 1-2 C ₁ -C ₆ alkyl group or acyl group The “aralkyl group” is also included. When the aralkyl group has a substituent, the substituent may be substituted on either or both of the aryl ring and the alkyl group constituting the aralkyl group.

In the present invention, “the same or different 1-2 C ₁ -C ₆ alkyl group, or an amino group optionally substituted with an acyl group” refers to the above “the same or different 1-2 C ₁ -C 6 _In addition to “amino group which may be substituted with ₆ alkyl groups”, it is an amino group substituted with 1 to 2 of the same or different “acyl group”, and examples thereof include dimethylamino group, diethylamino group, and acetylamino group. can do.

In the present invention, “a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group and a carbon atom to which R b and R c or R b and R c are bonded together or alkylene, same or different 1-3 is substituted with a substituent which may C ₃ -C ₁₀ cycloalkyl ring selected from the group consisting of phenoxy group "includes, in addition of the" C ₃ -C ₁₀ cycloalkyl group ", the same Or the above-mentioned “C ₃ -C ₁₀ cycloalkyl group” substituted by 1 to 3 different halogen atoms, or the above-mentioned “C ₃ -C ₆ alkyl group” substituted by ₁ to 3 of the same or different “C ₁ -C ₆ alkyl group” “C ₃ -C ₁₀ cycloalkyl group”, the above “C ₃ -C ₁₀ cycloalkyl group” substituted with ₁ to 3 of the same or different “C ₁ -C ₆ alkoxy group”, substituted with a phenoxy group Is The "C ₃ -C ₁₀ cycloalkyl group", and substituted a halogen atom, a C ₁ -C ₆ alkyl group, by two or more substituents selected from the group consisting of the C ₁ -C ₆ alkoxy group and phenoxy group The above-mentioned “C ₃ -C ₁₀ cycloalkyl group” is also included.

  X can be substituted at 1 to 4 substitutable positions on the quinolinone ring, and when two or more X are present, they may be the same or different.

  Y can be substituted at 1 to 6 substitutable positions on the quinoline ring, and when two or more Y are present, they may be the same or different.

In the compound (I) of the present invention,
(1) Ra, Rb, Rc, and Rd are preferably selected from the group consisting of a hydrogen atom; a halogen atom; a C _{2 to} C ₇ alkoxycarbonyl group; a halogen atom, a hydroxyl group, a C _{1 to} C ₆ alkoxy group, and a phenoxy group. C ₁ -C ₆ alkyl group which may be substituted with the same or different 1 to 3 substituents selected; halogen atom, C ₁ -C which may be substituted with 1 to 3 different halogen atoms _An aryl group which may be substituted with 1 to 5 substituents selected from the group consisting of ₆ alkyl groups, C ₁ -C ₆ alkoxy groups, nitro groups, cyano groups and hydroxyl groups, more preferably a hydrogen atom, a C ₂ -C ₃ alkoxycarbonyl group, the same or different 1-3 and which may be C ₁ -C ₄ alkyl group substituted with a halogen atom, still more preferably a hydrogen atom, methylcarbamoyl Group, an ethyl group, a propyl group, an ethoxycarbonyl group,
(2) X _m is preferably X is a halogen atom, a C _{1 to} C ₆ alkyl group or a C _{1 to} C ₆ alkoxy group that may be substituted with 1 to 3 halogen atoms that are the same or different. , M is 0 to 2, more preferably X is a fluorine atom, a chlorine atom, a methyl group or a methoxy group, m is 0, 1 or 2;
(3) Y _n is preferably Y is a fluorine atom, a chlorine atom or a methyl group, n is 0 or 1, and more preferably Y is a methyl group, and n is 0 or 1.

In the compound (I) of the present invention, preferably,
(A1) Ra, Rb, Rc and Rd may be the same or different and are a hydrogen atom; a halogen atom; a C _{2 to} C ₇ alkoxycarbonyl group; a halogen atom, a hydroxyl group, a C _{1 to} C ₆ alkoxy group and a phenoxy. A C ₁ -C ₆ alkyl group which may be substituted with the same or different 1 to 3 substituents selected from the group consisting of groups; a halogen atom, which may be substituted with the same or different 1 to 3 halogen atoms C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group, a nitro group, a cyano group, or an aryl group substituted with same or different 1 to 5 substituents selected from the group consisting of hydroxyl,
(A2) _{X m} is X is identical or different and have well, a halogen atom, the same or different 1-3 is substituted with a halogen atom or C ₁ -C ₆ alkyl group, C ₁ -C ₆ alkoxy group, C ₂ -C ₃ alkoxycarbonyl group, m is 0-2,
(A3) Y _n is Y is a fluorine atom, a chlorine atom or a methyl group, n is 0 or 1,
More preferably,
(B1) Ra, Rb, Rc , Rd are the same or different and have good hydrogen atom, C ₂ -C ₃ alkoxycarbonyl group, it may be substituted with same or different 1 to 3 halogen atoms C a ₁ -C ₄ alkyl group,
(B2) X _m is a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group, or a C ₂ -C ₃ which may be substituted with 1 to 3 halogen atoms that are the same or different. An alkoxycarbonyl group, m is from 0 to 2,
(B3) Y _n is Y is a fluorine atom, a chlorine atom or a methyl group, n is 0 or 1,
Even more preferably,
(C1) Ra, Rb, Rc, Rd are a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an ethoxycarbonyl group,
(C2) X _m is X is a fluorine atom, a chlorine atom, a methyl group or a methoxy group, m is 0, 1 or 2;
(C3) Y _n is Y is a methyl group, and n is 0 or 1.

  The compound (I) of the present invention can be converted to a salt such as sulfate, hydrochloride, nitrate and phosphate. Those salts are included in the present invention as long as they can be used as agricultural and horticultural fungicides.

  The compound (I) of the present invention and a salt thereof can be solvated, and these solvates are also encompassed in the present invention. Such solvates are preferably hydrates.

  The compound (I) of the present invention includes a compound having an asymmetric carbon. In this case, the present invention includes a mixture of one kind of optically active substance and several kinds of optically active substances. .

  Representative compounds of the present invention are exemplified in the following table, but the present invention is not limited to these compounds.

  Hereinafter, “Me” represents a methyl group, “Et” represents an ethyl group, “Pr” represents a propyl group, “iPr” represents an isopropyl group, “Bu” represents a butyl group, “iBu” represents an isobutyl group, “TBu” represents a tbutyl group, “Vinyl” represents a vinyl group, “Allyl” represents an allyl group, “Ethynyl” represents an ethynyl group, “Propar” represents a propargyl group, “Ph” represents a phenyl group, “ “2-Fur” represents a 2-furyl group, “2-Thi” represents a 2-thienyl group, “3-Pyd” represents a 3-pyridyl group, “Ac” represents an acetyl group, and “Bn” represents a benzyl group. , “CPen” forms a ring with Ra and Rb, Rc and Rd or Rb and Rc to form a cyclopentyl group, and “cHex” forms a ring with Ra and Rb, Rc and Rd, or Rb and Rc to form cyclohexyl The group “cHep” is Ra Rb, cycloheptyl group form a ring with Rc and Rd or Rb and Rc, the "H" is m = 0 and n = 0 in the "Xm" and "Yn", respectively.

Among the above exemplified compounds, preferred compounds are compound numbers 2, 7, 8, 9, 11, 39, 60, 61, 62, 64, 69, 76, 88, 89, 92, 113, 115, 117, 129. 142, 145, 161, 248, 251, 288, 410, 619, 622, 724, 725, 778, 781, 956, 961 or 1226,
More preferably, the compound No. 89, 92, 117, 142, 145, 248, 251, 619, 622, 725 or 956 is used.

The 3,4-dihydrobiquinolin-2-one compound of the present invention can be produced by Method A, Method B and Method C described below.
(Method A)

In the above formula, Ra, Rb, Rc, Rd, X, m, Y, n are as defined above, and Z is a chlorine atom, bromine atom, iodine atom, OSO ₂ CF ₃ group or B (OH) ₂ is shown.

  Method A is a method for producing the compound (I) of the present invention by reacting the 3,4-dihydroquinolinone compound (II) with the quinoline compound (III).

(Process A)
In step A, compound (II) of the present invention is produced by reacting compound (II) with compound (III) in a solvent or non-solvent in the presence of a metal catalyst, in the presence or absence of a base. It is a process to do.
When a solvent is used in this step, the solvent used is not particularly limited as long as it does not inhibit the reaction. For example, hydrocarbons such as hexane, cyclohexane, benzene, toluene, xylene; dichloromethane, dichloroethane, chloroform, Halogenated hydrocarbons such as carbon tetrachloride; Ethers such as dioxane, diethyl ether, tetrahydrofuran (THF) and dibutyl ether; Nitriles such as acetonitrile and propionitrile; Dimethylformamide (DMF), Dimethylacetamide (DMA), Amides such as N-methylpyrrolidone (NMP) or the like; or a mixed solvent thereof, preferably hydrocarbons or amides, more preferably toluene or N-methylpyrrolidone ( NMP).

  The metal catalyst used in this step is not particularly limited as long as it is used in a normal coupling reaction. For example, the metal catalyst may be a metal salt such as nickel, palladium, copper, or chromium, or a metal complex. Is tetrakistriphenylphosphine palladium or copper iodide.

  The amount of the metal catalyst used in this step is usually 0.001 to 2 mol, and preferably 0.1 to 0.5 mol, per 1 mol of compound (II).

  When a base is used in this step, the base to be used is not particularly limited as long as it is used as a base in a normal reaction. For example, alkali metal carbonates such as sodium carbonate and potassium carbonate; sodium bicarbonate Alkali metal hydrogen carbonates such as potassium hydrogen carbonate; alkali metal hydroxides or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, barium hydroxide; sodium methoxide, sodium ethoxide, potassium Alkali metal alkoxides such as t-butoxide; triethylamine, tributylamine, diisopropylethylamine, N-methylmorpholine, pyridine, 4- (N, N-dimethylamino) pyridine, N, N-dimethylaniline, N, N-diethyl Aniline, 1,5-diazabicyclo 4.3.0] non-5-ene, 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) Organic bases, preferably alkali metal carbonates, organic bases, or alkali metal hydroxides, more preferably sodium carbonate, potassium carbonate, pyridine, triethylamine, or sodium hydroxide. .

  The amount of the base used is usually 1 to 6 mol, preferably 1.1 to 3 mol, per 1 mol of compound (II).

  The reaction temperature varies depending on the raw material compound, reaction reagent, solvent and the like, but is usually 50 ° C to 300 ° C, and preferably 80 ° C to 250 ° C.

  While the reaction time varies depending on the raw material compound, reaction reagent, solvent, reaction temperature and the like, it is generally 15 minutes to 120 hours, preferably 30 minutes to 10 hours.

  The 3,4-dihydroquinolinone compound (II) which is a starting material of the above-mentioned method A is a known compound or a known method {for example, Chem. Ber., 1887, 20 vol.441, J. Med. Chem., 1997, 40, 3567, or Eur. J. Med. Chem. Chim. Ter., 1983, page 107}.

The quinoline compound (III) used in this step is a known compound or a known method {for example, J. Chem. Soc., 1935, page 1425, J. Am. Chem. Soc., 1955, 77, p. 4175, or J. Org. Chem., 2002, 67, p. 5394}.
(Method B)

In the above formula, Rc, Rd, X, m, Y, n are as defined above, and Ra ′ is a hydrogen atom, a C ₁ -C ₆ alkoxy group; an acyl group; a cyano group; an acyloxy group; a halogen atom , C ₁ -C ₆ alkoxy group, C ₁ -C ₆ same or different 1-3 is substituted with a substituent C ₁ may -C ₆ alkyl group selected from alkylthio, and the group consisting of a phenoxy group, a halogen atoms, the same or different 1-3 which may be substituted C ₁ -C ₆ alkyl group by a halogen atom, C ₁ -C ₆ alkoxy group, the same or different 1 to 5 selected from cyano group, consisting of the group An aryl group which may be substituted with 1 substituent; a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group which may be substituted with the same or different 1 to 3 halogen atoms, a cyano group Chosen from the group Shows the same or different 1 to 6 substituents which may be substituted aralkyl group group, Rb 'is halogen atom, a hydroxyl group, an acyl group, a carboxyl group, a halogen atom, a hydroxyl group, C ₁ -C ₆ alkoxy groups, C _{1 to} C ₆ alkylthio group, C _{1 to} C ₆ alkylsulfinyl group, C _{1 to} C ₆ alkylsulfonyl group, and C which may be substituted with 1 to 3 different substituents selected from the group consisting of phenoxy group ₁ -C ₆ alkyl group; a halogen atom, a hydroxyl group, C ₁ -C ₆ alkoxy group, C ₁ -C ₆ alkylthio group, C ₁ -C ₆ alkylsulfinyl group, C ₁ -C ₆ alkylsulfonyl group, a phenyl group and phenoxy same or different 1-3 is substituted with a substituent or C ₂ to -C ₆ alkenyl group selected from the group consisting of groups; halogen atoms, hydroxyl, C ₁ -C ₆ a Kokishi group, C ₁ -C ₆ alkylthio group, C ₁ -C ₆ alkylsulfinyl group, C ₁ -C ₆ alkylsulfonyl group, the same or different 1-3 substituents selected from the group consisting of phenyl and phenoxy groups which may be substituted C ₂ -C ₆ alkynyl group group; a halogen atom, the same or different 1 to 3 may C ₁ -C ₆ alkyl group substituted by a halogen atom, C ₁ -C ₆ alkoxy group, a nitro The same or different ₁ to ₆ substituents selected from the group consisting of a group, a cyano group, a hydroxyl group and an amino group which may be substituted with the same or different 1 to 2 C ₁ -C ₆ alkyl group or acyl group (In the compound (Ia), when Ra ′ is a hydrogen atom, the compound (Ib) can be monosubstituted or disubstituted by Rb ′)) Is formed together with the carbon atom to which Ra and Rb are bonded, a halogen atom, C ₁ -C ₆ alkyl group, C ₁ -C ₆ same or different 1 to selected from the alkoxy group and the group consisting of a phenoxy group Represents a C ₃ -C ₁₀ cycloalkyl ring which may be substituted with three substituents, and L represents a leaving group.

(Process B)
Method B is a method for producing the compound (Ib) of the present invention by reacting the compound (Ia) of the present invention with an electrophile in the presence of a base.

  The base used in this step is not particularly limited as long as it is used as a base in a normal reaction. For example, alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium t-butoxide; triethylamine , Tributylamine, diisopropylethylamine, N-methylmorpholine, pyridine, 4- (N, N-dimethylamino) pyridine, N, N-dimethylaniline, N, N-diethylaniline, 1,5-diazabicyclo [4.3. Organic bases such as 0] non-5-ene, 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) Hydrides such as lithium hydride, sodium hydride, potassium hydride; lithium dii Like propylamide (LDA), lithium = 2,2,6,6-tetramethylpiperidide (LTMP), lithium = hexamethyldisilazide, sodium = hexamethyldisilazide, potassium = hexamethyldisilazide Metal amides, preferably organic bases, hydrides or metal amides, more preferably triethylamine, sodium hydride, lithium diisopropylamide (LDA) or lithium = hexamethyldisilazide It is.

  The amount of the base to be used is usually 1 to 10 mol, preferably 1.1 to 3 mol, per 1 mol of compound (Ia).

  The reaction temperature varies depending on the raw material compound, the reaction reagent, the solvent, and the like, but is usually −100 ° C. to 100 ° C., and preferably −80 ° C. to 20 ° C.

  While the reaction time varies depending on the raw material compound, reaction reagent, solvent, reaction temperature and the like, it is usually 5 minutes to 10 hours, preferably 10 minutes to 3 hours.

  The solvent used in this step is not particularly limited as long as it does not inhibit the reaction. For example, hydrocarbons such as hexane, cyclohexane, benzene, toluene, xylene; dichloromethane, dichloroethane, chloroform, carbon tetrachloride, etc. Halogenated hydrocarbons; ethers such as dioxane, diethyl ether, tetrahydrofuran (THF), dibutyl ether; amides such as dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone (NMP), etc .; or These may be a mixed solvent, preferably ethers or amides, and more preferably tetrahydrofuran (THF) or dimethylformamide (DMF).

  Compound (Ia) which is a starting material of the above-mentioned method B can be produced by the above-mentioned method A.

上式中、Ｒａ、Ｒｂ、Ｒｃ、Ｒｄ、Ｘ、ｍ、Ｙ、ｎは、前記と同意義を示し、
Ｘａは、ハロゲン原子；水酸基；Ｃ₁〜Ｃ₆アルコキシ基；アシル基；カルボキシル基；シアノ基；アシルオキシ基；ニトロ基；Ｃ₁〜Ｃ₆アルキルチオ基；ハロゲン原子、水酸基及びＣ₁〜Ｃ₆アルキルチオ基からなる群から選ばれる同一若しくは異なった１〜３個の置換基で置換されてよいＣ₁〜Ｃ₆アルキル基；ハロゲン原子、水酸基及びＣ₁〜Ｃ₆アルキルチオ基からなる群から選ばれる同一若しくは異なった１〜３個の置換基で置換されてよいＣ₂〜Ｃ₆アルケニル基；ハロゲン原子、水酸基及びＣ₁〜Ｃ₆アルキルチオ基からなる群から選ばれる同一若しくは異なった１〜３個の置換基で置換されてよいＣ₂〜Ｃ₆アルキニル基；ハロゲン原子、同一若しくは異なった１〜３個のハロゲン原子で置換されてよいＣ₁〜Ｃ₆アルキル基、Ｃ₁〜Ｃ₆アルコキシ基、ニトロ基、シアノ基、水酸基及び同一若しくは異なった１〜２個のＣ₁〜Ｃ₆アルキル基又はアシル基で置換されてよいアミノ基からなる群から選ばれる同一若しくは異なった１〜６個の置換基で置換されてよいアリール基；ハロゲン原子、同一若しくは異なった１〜３個のハロゲン原子で置換されてよいＣ₁〜Ｃ₆アルキル基及びＣ₁〜Ｃ₆アルコキシ基からなる群から選ばれる同一若しくは異なった１〜６個の置換基で置換されてよいヘテロアリール基；同一若しくは異なった１〜２個のＣ₁〜Ｃ₆アルキル基若しくはアシル基で置換されてよいアミノ基を示し、
Ｘｂは、Ｘと同意義を示す。
Ｃ法は、一般式（Ｉｃ）で表される化合物の特定の置換基を、他の置換基に変換し、一般式（Ｉｄ）で表される本発明化合物を製造する方法である。 (Method C)

In the above formula, Ra, Rb, Rc, Rd, X, m, Y, n are as defined above,
Xa is halogen atom; hydroxyl group; C ₁ -C ₆ alkoxy group; acyl group; carboxyl group; cyano group; acyloxy group; nitro group; C ₁ -C ₆ alkylthio group; halogen atom, hydroxyl group and C ₁ -C ₆ alkylthio A C ₁ -C ₆ alkyl group which may be substituted with the same or different 1 to 3 substituents selected from the group consisting of groups; the same selected from the group consisting of halogen atoms, hydroxyl groups and C ₁ -C ₆ alkylthio groups Or a C ₂ -C ₆ alkenyl group which may be substituted with 1 to 3 different substituents; the same or different 1 to 3 selected from the group consisting of a halogen atom, a hydroxyl group and a C ₁ -C ₆ alkylthio group it may be substituted with a substituent C ₂ -C ₆ alkynyl group; a halogen atom, the same or different 1-3 is substituted with a halogen atom or C ₁ -C ₆ alkyl group, ₁ -C ₆ alkoxy group, a nitro group, the same or different selected from cyano group, hydroxy group and the same or different one to two C ₁ -C ₆ alkyl group or a group consisting of or an amino group substituted with an acyl group An aryl group which may be substituted by 1 to 6 substituents; a halogen atom, a C ₁ -C ₆ alkyl group and a C ₁ -C ₆ alkoxy group which may be substituted by 1 to 3 halogen atoms which are the same or different A heteroaryl group which may be substituted with the same or different 1 to 6 substituents selected from the group consisting of: may be substituted with the same or different 1 to 2 C ₁ -C ₆ alkyl groups or acyl groups Represents an amino group,
Xb has the same meaning as X.
Method C is a method for producing the compound of the present invention represented by the general formula (Id) by converting a specific substituent of the compound represented by the general formula (Ic) into another substituent.

(Process C)
Step C is a step for producing the compound (Id) of the present invention by converting the compound (Ic) to a functional group.
The functional group conversion in this step can be performed by a method generally known as a functional group conversion reaction, for example, a halogen atom to a cyano group, a halogen atom to an amino group, a halogen atom to an alkoxy group, or a halogen atom to an alkylthio group. , Hydroxyl group to acyloxy group, amino group to acylamide group, amino group to diazonium salt to halogen atom, amino group to diazonium salt to cyano group, amino group to diazonium salt to hydroxyl group, nitro group to amino group, carboxyl Group to alkoxycarbonyl group, alkoxycarbonyl group to carboxyl group, cyano group to carboxyl group, cyano group to carbamoyl group, carbamoyl group to cyano group, chloroalkyl group or bromoalkyl group to alkoxyalkyl group, chloro From alkyl group or bromoalkyl group to alkylthioalkyl group, alkylthio group to alkylsulfinyl group or alkylsulfonyl group, acyl group to hydroxyalkyl group, hydroxyalkyl group to acyl group or carboxyl group, halogen atom to alkenyl group, halogen atom to alkynyl group And a halogen atom to an aryl group, a halogen atom to a heteroaryl group, and the like.
This step can be performed according to, for example, the Chemical Society of Japan, Experimental Chemistry Course Volumes 19 to 26, Organic Synthesis (1990), Maruzen, Tokyo.
Compound (Ic) which is a starting material of the above-mentioned method C can be produced by the above-mentioned method A or B.

  After completion of each of the above reactions, the target compound of each reaction can be collected from the reaction mixture according to a conventional method. For example, the reaction mixture is appropriately neutralized, and if insoluble matter is present, it is removed by filtration, water and an immiscible organic solvent such as ethyl acetate are added, and after washing with water, the organic layer containing the target compound is removed. After separating and drying over anhydrous magnesium sulfate or the like, the solvent is distilled off.

  If necessary, the obtained target compound can be further purified by a conventional method such as recrystallization, reprecipitation or chromatography.

  The step of producing the salt of the compound (I) of the present invention comprises an extraction concentrate of the reaction mixture containing the compound (I) produced in each step or a solution obtained by dissolving the compound (I) in a suitable solvent. Is done by adding

Acids used in the reaction are hydrohalic acid such as hydrofluoric acid, hydrochloric acid, hydrobromic acid and hydroiodic acid, inorganic acids such as nitric acid, perchloric acid, sulfuric acid and phosphoric acid; methanesulfonic acid , Lower alkyl sulfonic acids such as trifluoromethanesulfonic acid and ethanesulfonic acid, arylsulfonic acids such as benzenesulfonic acid and p-toluenesulfonic acid, organic acid salts such as succinic acid and oxalic acid; and organic acids such as saccharin There may be mentioned acid amide compounds.
The acid is usually used in an amount of 1 equivalent to 10 equivalents, preferably 1 equivalent to 5 equivalents.

  The solvent used in the reaction is not particularly limited as long as it does not inhibit the reaction, and preferably includes ethers such as ether, diisopropyl ether, tetrahydrofuran (THF) and dioxane, and alcohols such as methanol and ethanol. Can do.

  The reaction temperature is -20 ° C to 50 ° C, preferably -10 ° C to 30 ° C.

  The reaction time varies depending on the type of solvent used and the temperature, but is usually 10 minutes to 1 hour.

  The resulting salt is isolated by conventional methods. That is, when it precipitates as a crystal, it is isolated by filtration, and when it is water-soluble, it is isolated as an aqueous solution by separation of an organic solvent and water.

  The compound of the present invention is useful as an active ingredient of a pest control agent. For example, as an agricultural and horticultural fungicide, it exhibits an excellent control effect against diseases caused by various plant pathogens. In particular, it exhibits an excellent control effect against various diseases such as rice blast, adzuki bean, tomato, cucumber, and kidney beans such as gray mold disease and mycorrhizal disease. Specific examples of pathogens include, for example, the rice blast Magnaporthe grisea, and the brown fungus Botrytis cinerea of azuki bean, tomato, cucumber and kidney beans and the sclerotia of these plants Examples include, but are not limited to, sclerotinia sclerotiorum. Since the compound of the present invention has an excellent therapeutic effect, disease control by treatment after infection is possible.

  When using the compound of the present invention, it can be formulated into various forms such as an emulsion, a powder, a wettable powder, a liquid, a granule, a suspension and the like together with an auxiliary agent as in the case of a conventional agricultural chemical formulation. In actual use of these preparations, they can be used as they are or diluted to a predetermined concentration with a diluent such as water.

  Examples of the auxiliary agent used include carriers, emulsifiers, suspension dispersants, spreading agents, wetting agents, thickeners, and the like, which can be appropriately added as necessary.

  The carriers used are divided into solid carriers and liquid carriers. Solid carriers are starch, sugar, cellulose powder, cyclodextrin, activated carbon, soybean powder, wheat flour, rice bran powder, wood powder, fish powder, milk powder, and other animal and vegetable powders. Or mineral powder such as talc, kaolin, bentonite, organic bentonite, calcium carbonate, calcium sulfate, sodium bicarbonate, zeolite, diatomaceous earth, white carbon, clay, alumina, silica, sulfur powder, etc., and the liquid carrier is Animal and vegetable oils such as soybean oil, nut oil and corn oil; Alcohols such as ethyl alcohol and ethylene glycol; Ketones such as acetone and methyl ethyl ketone; Ethers such as dioxane and tetrahydrofuran; Kerosene, kerosene, liquid paraffin, Xylene, trimethylbenzene, tetrame Aliphatic / aromatic hydrocarbons such as rubenzene, cyclohexane and solvent naphtha; Halogenated hydrocarbons such as chloroform and chlorobenzene; Acid amides such as dimethylformamide; Esters such as ethyl acetate and glycerol ester of fatty acid; Acetonitrile Nitriles such as; sulfur-containing compounds such as dimethyl sulfoxide; or N-methylpyrrolidone.

  The type of emulsifier is not particularly limited as long as it is usually used in the production of agrochemical compositions, but it is possible to select an emulsifier that has the ability to stably emulsify poorly water-soluble agrochemical components as fine particles in water. desirable. Preferably, low-sulfated oil, calcium alkylbenzenesulfonate, petroleum sulfonate, soap (sodium and organic amine salt), higher alcohol sulfate ester salt, dodecylbenzenesulfonate, fatty acid monoglyceride, span type nonionic emulsifier, higher alcohol Ethylene oxide 3 to 6 mol adduct, alkylphenol ethylene oxide 3 to 6 mol adduct, polyethylene glycol fatty acid ester, tween type nonionic emulsifier or higher alcohol ethylene oxide 8 to 20 mol adduct, or an emulsifier having performance equivalent thereto Can be used. These emulsifiers may be used alone or in combination of two or more.

As the wetting agent, a surfactant can be used, but the kind thereof is not particularly limited, and any wetting agent usually used in the field of agricultural chemicals can be used. The wetting agent has an effect of improving the adhesion of the diluted solution to the target when a water diluted solution obtained by diluting the composition with water is sprayed on the target soil or plant. The surfactant used as the wetting agent may be any of anionic, cationic, nonionic or amphoteric surfactants, for example. Two or more surfactants may be used in combination as the wetting agent.
Anionic surfactants used as wetting agents include alkyl phosphate ester salts, alkyl sulfate ester salts, polyoxyalkylene alkyl ether phosphate ester salts, polyoxyethylene alkyl ether sulfate ester salts, alkylaryl phosphate ester salts, alkylaryl sulfates Ester salt, polyoxyalkylene alkylaryl ether phosphate ester salt, polyoxyalkylene alkylaryl ether sulfate ester salt, alkylphenol phosphate salt, alkylphenol phosphate ester salt, alkylphenol sulfate salt, alkylphenol sulfate ester salt, polyoxyalkylene alkylphenol phosphate salt, polyoxy Alkylene alkylphenol phosphate salt, polyoxyalkylene alkylphenol sulfate, polyoxyal Lenalkylphenol sulfate, styrylphenol phosphate, styrylphenol phosphate, styrylphenol sulfate, styrylphenol sulfate, polyoxyalkylene styrylphenol phosphate, polyoxyalkylene styrylphenol phosphate, polyoxyalkylene styrylphenol Sulfate, polyoxyalkylene styrylphenol sulfate, distyrylphenol phosphate, distyrylphenol phosphate, distyrylphenol sulfate, distyrylphenol sulfate, polyoxyalkylene distyrylphenol phosphate, polyoxyalkyl Range styrylphenol phosphate, polyoxyalkylene distyrylphenol sulfate, polyoxyalkylene disty Ruphenol sulfate ester salt, tristyryl phenol phosphate salt, tristyryl phenol phosphate ester salt, tristyryl phenol sulfate salt, tristyryl phenol sulfate ester salt, polyoxyalkylene tristyryl phenol phosphate salt, polyoxyalkylene tristyryl phenol phosphate ester salt And polyoxyalkylene tristyrylphenol sulfate, polyoxyalkylene tristyrylphenol sulfate, alkyl succinate sulfonate, dialkyl succinate sulfonate, and polyoxyalkylene dialkyl succinate sulfonate. Examples of cationic surfactants used as wetting agents include aliphatic tertiary amines or salts thereof, aliphatic tertiary amines aliphatic amine alkylene oxide adducts or salts thereof, or aliphatic quaternary amine salts. be able to.
Nonionic surfactants used as wetting agents include aliphatic alcohol alkylene oxide adducts, polyalkyleneoxy fatty acid esters, sorbitan surfactants or their alkylene oxide adducts, polyglycerin fatty acid esters, alkylpolysaccharide surfactants. Agent, shuroglyceride, polyoxyalkylene alkyl ether, polyoxyethylene alkyl ether, polyoxyalkylene alkyl aryl ether, polyoxyalkylene alkyl phenol ether, polyoxyalkylene styryl phenol ether, polyoxyalkylene distyryl phenol ether, or polyoxyalkylene And tristyrylphenol ether.

  The kind of suspension dispersant to be used is not particularly limited, and any spreading agent usually used in the field of agricultural chemicals can be used. For example, formalin condensate of alkyl naphthalene sulfonate, lignin sulfonate, alkyl aryl sulfonate, carboxymethyl cellulose, polyacrylate, polycarboxylate, polyoxyethylene polyoxypropylene block polymer, polystyrene polyoxyethylene block Examples thereof include anionic surfactants such as polymers, polyvinyl pyrrolidone and methoxypolyethylene oxide methacrylate, gum arabic, xanthan gum and titanium oxide.

The type of thickener used is not particularly limited. For example, in addition to a thickener usually used in the field of agricultural chemicals, a substance having a thickening action generally used as an anti-caking agent or an anti-settling agent for emulsions, Any substance that can be used as a thickener in other fields such as food or pharmaceuticals can be used. For example, white carbon, gum arabic, gum tragacanth, xanthan gum, guar gum, roast bean gum, casein, alginic acid, cellulosic polysaccharide, ethyl cellulose, polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, aluminosilicate, bentonite Montmorillonite, hectorite, attapulgite and the like. These thickeners may be used alone, or two or more thickeners may be used in combination.

  The kind of spreading agent to be used is not particularly limited, and any spreading agent usually used in the field of agricultural chemicals can be used. The spreading agent spreads and adheres to the plant in contact with the plant by applying and spraying the agrochemical formulation, enhances adhesion, imparts rain resistance and the like, and has an action of increasing penetration into the plant body and pests. For example, paraffin, casein lime, alkyltrimethylammonium chloride, sodium dialkylsulfosuccinate, sodium dioctylsulfosuccinate, sodium dodecylbenzenesulfonate, sodium polyacrylate, polyalkylene glycol alkyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl Ether, polyoxyethylene octylphenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene resin acid ester, polyoxyethylene dodecyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene hexitan fatty acid ester, polyvinyl acetate, D-sorbit And so on.

  The compounding mass ratio of the compound of the present invention and the adjuvant is usually 0.05: 99.95 to 90:10, and preferably 0.2: 99.8 to 80:20.

  The concentration or amount used of the compound of the present invention varies depending on the target crop, method of use, formulation, application rate, etc., but in the case of foliage treatment, it is usually 0.1 to 10000 ppm per active ingredient, preferably 1 In the case of soil treatment, it is usually 10 to 100,000 g / ha, preferably 100 to 10,000 g / ha.

  The compound of the present invention may be used in combination or in combination with other agricultural chemicals such as insecticides, acaricides, attractants, nematicides, fungicides, antiviral agents, herbicides, plant growth regulators, etc. as necessary. Preferred are insecticides, acaricides, nematicides or fungicides.

  The insecticide, acaricide or nematicide used is, for example, O- (4-bromo-2-chlorophenyl) O-ethyl S-propyl phosphorothioate (generic name: propenophos), O- (2,2-dichlorovinyl). ) O, O-dimethyl phosphate (generic name: dichlorophos), O-ethyl O- {3-methyl-4- (methylthio) phenyl} N-isopropyl phosphoramidate (generic name: phenamiphos), O, O-dimethyl O- (4-nitro-m-tolyl) phosphorothioate (generic name: fenitrothion), O-ethyl O- (4-nitrophenyl) phenylphosphonothioate (generic name: EPN), O, O-diethyl O- (2 -Isopropyl-6-methylpyrimidin-4-yl) phosphorothioate (generic name: diazinon), O, O-dimethyl -(3,5,6-trichloro-2-pyridyl) phosphorothioate (generic name: chlorpyrifosmethyl), O, S-dimethyl N-acetylphosphoramidothioate (generic name: acephate), O- (2,4- Organophosphate compounds such as dichlorophenyl) O-ethyl S-propyl phosphorodithioate (generic name: prothiophos); 1-naphthyl N-methylcarbamate (generic name: carbaryl), 2-isopropoxyphenyl N-methyl Carbamate (generic name: propoxyl), 2-methyl-2- (methylthio) propionaldehyde O-methylcarbamoyloxime (generic name: aldicarb), 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-methyl Carbamate (generic name: carbofuran), dimethyl N, N '-[Thiobis {(methylimino) carbonyloxy}] bisethaneimidothioate (generic name: thiodicarb), S-methyl N- (methylcarbamoyloxy) thioacetimidate (generic name: mesomil), N, N-dimethyl 2-methylcarbamoyloxyimino-2- (methylthio) acetamide (generic name: oxamyl), 2- (ethylthiomethyl) phenyl N-methylcarbamate (generic name: etiophencarb), 2-dimethylamino-5,6-dimethyl Carbamate compounds such as pyrimidin-4-yl N, N-dimethylcarbamate (generic name: pyrimicarb), 2-sec-butylphenyl N-methylcarbamate (generic name: fenocarb); S, S′-2-dimethylamino Trimethylenebis (thiocarbamate) (one Generic name: Cartap), nereistoxin compounds such as N, N-dimethyl-1,2,3-trithian-5-ylamine (generic name: thiocyclam); 2,2,2-trichloro-1,1-bis Organochlorine compounds such as (4-chlorophenyl) ethanol (generic name: dicophore), 4-chlorophenyl-2,4,5-trichlorophenylsulfone (generic name: tetradiphone); bis {tris (2-methyl-2- Organometallic compounds such as (phenylpropyl) tin} oxide (generic name: phenbutadium oxide); (RS) -α-cyano-3-phenoxybenzyl (RS) -2- (4-chlorophenyl) -3-methylbutyrate (Generic name: fenvalerate), 3-phenoxybenzyl (1RS) -cis, trans-3- (2,2-dichlorovinyl) -2, -Dimethylcyclopropanecarboxylate (generic name: permethrin), (RS) -α-cyano-3-phenoxybenzyl (1RS) -cis, trans-3- (2,2-dichlorovinyl) -2,2-dimethylcyclo Propanecarboxylate (generic name: cypermethrin), (S) -α-cyano-3-phenoxybenzyl (1R) -cis-3- (2,2-dibromovinyl) -2,2-dimethylcyclopropanecarboxylate ( (Generic name: deltamethrin), (RS) -α-cyano-3-phenoxybenzyl (1RS) -cis, trans-3- (2-chloro-3,3,3-trifluoropropenyl) -2,2-dimethylcyclo Propanecarboxylate (generic name: cyhalothrin), 4-methyl-2,3,5,6-tetrafluorobenzyl-3- (2 -Chloro-3,3,3-trifluoro-1-propenyl) -2,2-dimethylcyclopropanecarboxylate (generic name: tefluthrin), 2- (4-ethoxyphenyl) -2-methylpropyl 3-phenoxybenzyl Pyrethroid compounds such as ether (generic name: etofenprox); 1- (4-chlorophenyl) -3- (2,6-difluorobenzoyl) urea (generic name: diflubenzuron), 1- [3,5-dichloro -4- (3-chloro-5-trifluoromethyl-2-pyridyloxy) phenyl] -3- (2,6-difluorobenzoyl) urea (generic name: chlorfluazuron), 1- (3,5- Dichloro-2,4-difluorophenyl) -3- (2,6-difluorobenzoyl) urea (generic name: teflubenzuron) A juvenile hormone-like compound such as isopropyl (2E, 4E) -11-methoxy-3,7,11-trimethyl-2,4-dotecadienoate (generic name: metoprene); Pyridazinone compounds such as t-butyl-5- (4-t-butylbenzylthio) -4-chloro-3 (2H) -pyridazinone (generic name: pyridaben); t-butyl 4-{(1,3- Pyrazole compounds such as dimethyl-5-phenoxypyrazol-4-yl) methyleneaminooxymethyl} benzoate (generic name: fenpyroximate); 1- (6-chloro-3-pyridylmethyl) -N-nitro-imidazolidine- Nitro compounds such as 2-ylideneamine (generic name: imidacloprid); dinitro compounds, organic sulfur compounds, urea Compounds, triazine compounds, hydrazine compounds, and other compounds such as 2-tert-butylimino-3-isopropyl-5-phenyl-3,4,5,6-tetrahydro-2H-1,3,5-thiadiazine -4-one (generic name: bubrophezine), trans- (4-chlorophenyl) -N-cyclohexyl-4-methyl-2-oxothiazolidinone-3-carboxamide (generic name: hexythiazox), N-methylbis (2, 4-Xylyliminomethyl) amine (generic name: amitraz), N ′-(4-chloro-o-tolyl) -N, N-dimethylformamidine (generic name: chlordimeform), (4-ethoxyphenyl)-{ 3- (4-Fluoro-3-phenoxyphenyl) propyl} (dimethyl) silane (generic name: silafluoff) Or the like. Furthermore, the compound of the present invention can be mixed and used in combination with microbial pesticides such as BT agents and entomopathogenic virus agents, and antibiotics such as avermectin and milbemycin.

  Examples of the bactericides used include 2-anilino-4-methyl-6- (1-propynyl) pyrimidine (generic name: mepanipyrim), 4,6-dimethyl-N-phenyl-2-pyrimidinamine (generic name: pyrimethanil). Pyrimidinamine compounds such as: 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) butanone (generic name: triazimephone), 1- ( Biphenyl-4-yloxy) -3,3-dimethyl-1- (1H, 1,2,4-triazol-1-yl) butan-2-ol (generic name: viteltanol), 1- {N- (4- Chloro-2-trifluoromethylphenyl) -2-propoxyacetimidoyl} imidazole (generic name: triflumizole), 1- {2- (2,4-dichlorophenyl) -4-ethyl-1,3-dioxolan-2-ylmethyl} -1H-1,2,4-triazole (generic name: ethaconazole), 1- {2- (2,4-dichlorophenyl) -4-propyl-1 , 3-Dioxolan-2-ylmethyl} -1H-1,2,4-triazole (generic name: propiconazole), 1- {2- (2,4-dichlorophenyl) pentyl} -1H-1,2,4 -Triazole (generic name: penconazole), bis (4-fluorophenyl) (methyl) (1H-1,2,4-triazol-1-ylmethyl) silane (generic name: flusilazole), 2- (4-chlorophenyl)- 2- (1H-1,2,4-triazol-1-ylmethyl) hexanenitrile (generic name: microbutanyl), (2RS, 3RS) -2- (4-chlorophene) ) -3-cyclopropyl-1- (1H-1,2,4-triazol-1-yl) butan-2-ol (generic name: cyproconazole), (RS) -1- (4-chlorophenyl) -4,4-dimethyl-3- (1H-1,2,4-triazol-1-ylmethyl) pentan-3-ol (generic name: terbuconazole), (RS) -2- (2,4-dichlorophenyl) ) -1- (1H-1,2,4-triazol-1-yl) hexan-2-ol (generic name: hexaconazole), (2RS, 5RS) -5- (2,4-dichlorophenyl) tetrahydro- 5- (1H-1,2,4-triazol-1-ylmethyl) -2-furyl 2,2,2-trifluoroethyl ether (generic name: farconazole cis), N-propyl-N- {2- (2,4,6- Trichlorophenoxy) ethyl} imidazole-1-carboxamide (generic name: prochloraz), 2- (4-fluorophenyl) -1- (1H-1,2,4triazol-1-yl) -3-trimethylsilylpropane-2- Azole compounds such as all (generic name: cimeconazole); quinoxaline compounds such as 6-methyl-1,3-dithiolo [4,5-b] quinoxalin-2-one (generic name: quinomethionate); Polymer of ethylene bis (dithiocarbamate) (generic name: mannebu), polymer of zinc ethylene bis (dithiocarbamate) (generic name: dinecarb), zinc (zinc) and Manganese ethylene bis (dithiocarbamate) (manneb) Complex compounds (generic name: manzeb), dizincbis (dimethyldithiocarbamate) G) Dithiocarbamate compounds such as ethylene bis (dithiocarbamate) (generic name: polycarbamate), polymer of zinc propylene bis (dithiocarbamate) (generic name: provineb); 4,5,6,7-tetrachloro Organochlorine compounds such as phthalide (generic name: fusalide), tetrachloroisophthalonitrile (generic name: chlorotalonyl), pentachloronitrobenzene (generic name: quintozen); methyl 1- (butylcarbamoyl) benzimidazole-2- Like irucarbamate (generic name: benomyl), dimethyl 4,4 '-(o-phenylene) bis (3-thioallophanate) (generic name: thiophanate methyl), methylbenzimidazol-2-ylcarbamate (generic name: carbendazim) Benzimidazole Such as 3-chloro-N- (3-chloro-2,6-dinitro-4-α, α, α-trifluorotolyl) -5-trifluoromethyl-2-pyridinamine (generic name: fluazinam) Pyridinamine compounds; cyanoacetamide compounds such as 1- (2-cyano-2-methoxyiminoacetyl) -3-ethylurea (generic name: simoxanyl); methyl N- (2-methoxyacetyl) -N- (2 , 6-Xylyl) -DL-alaninate (generic name: metalaxyl), 2-methoxy-N- (2-oxo-1,3-oxazolidine-3-yl) aceto-2 ′, 6′-xylide (generic name: Oxadixyl), (±) -α-2-chloro-N- (2,6-xylylacetamido) -γ-butyrolactone (generic name: off-race), methyl N-phenylacetyl- N- (2,6-xylyl) -DL-alaninate (generic name: benalaxyl), methyl N- (2-furoyl) -N- (2,6-xylyl) -DL-alaninate (generic name: flaxyl), ( Phenylamide compounds such as ±) -α- [N- (3-chlorophenyl) cyclopropanecarboxamide] -γ-butyrolactone (generic name: cyprofuran); N-dichlorofluoromethylthio-N ′, N′-dimethyl-N -Sulfenic acid-based compounds such as phenylsulfamide (generic name: dichlorfluanide); cupric hydroxide (generic name: cupric hydroxide), copper 8-quinolinolate (generic name: organic copper) Copper-based compounds; isoxazole-based compounds such as 5-methylisoxazol-3-ol (generic name: hydroxyisoxazole); aluminum Tris (ethyl phosphonate) (generic name: fosetyl aluminum), O-2,6-dichloro-p-tolyl-O, O-dimethyl phosphorothioate (generic name: tolcrophos-methyl), S-benzyl O, O-diisopropyl phosphorothioate, Organophosphorus compounds such as O-ethyl S, S-diphenyl phosphorodithioate and aluminum ethyl hydrogen phosphonate; N- (trichloromethylthio) cyclohexyl-4-ene-1,2-dicarboximide (generic name: captan) N- (1,1,2,2-tetrachloroethylthio) cyclohexyl-4-ene-1,2-dicarboximide (generic name: captaphor), N- (trichloromethylthio) phthalimide (generic name: folpette) Such N-halogenothioalkyl compounds; N (3,5-dichlorophenyl) -1,2-dimethylcyclopropane-1,2-dicarboximide (generic name: procymidone), 3- (3,5-dichlorophenyl) -N-isopropyl-2,4-dioxo Imidazolidine-1-carboxamide (generic name: iprodione), (RS) -3- (3,5-dichlorophenyl) -5-methyl-5-vinyl-1,3-oxazolidine-2,4-dione (generic name: Dicarboximide compounds such as vinclozoline); α, α, α-trifluoro-3′-isopropoxy-o-toluanilide (generic name: flutolanil), 3′-isopropoxy-o-toluanilide (generic name: mepronil) Benzanilide compounds such as); N, N ′-[piperazine-1,4-diylbis {(trichloromethyl) methylene}] Piperazine compounds such as formamide (generic name: triphorin); pyridine compounds such as 2 ′, 4′-dichloro-2- (3-pyridyl) acetophenone O-methyloxime (generic name: pyrifenox); ±) -2,4′-dichloro-α- (pyrimidin-5-yl) benzhydryl alcohol (generic name: phenalimol), (±) -2,4′-difluoro-α- (1H-1,2, Carbinol compounds such as 4-triazol-1-ylmethyl) benzhydryl alcohol (generic name: flutriaphor); (RS) -1- {3- (4-t-butylphenyl) -2-methylpropyl } Piperidin compounds such as piperidine (generic name: phenpropidin); (±) -cis-4- {3- (4-t-butylphenyl) -2-methylpropyl Morpholine compounds such as -2,6-dimethylmorpholine (generic name: fenpropimorph); triphenyltin hydroxide (generic name: fentin hydroxide), triphenyltin acetate (generic name: fentin acetate) ) Organotin compounds such as 1) -urea compounds such as 1- (4-chlorobenzyl) -1-cyclopentyl-3-phenylurea (generic name: pencyclone); (E, Z) 4- {3- ( Synthetic acid compounds such as 4-chlorophenyl) -3- (3,4-dimethoxyphenyl) acryloyl} morpholine (generic name: dimethomorph); isopropyl 3,4-diethoxycarbanilate (generic name: dietofencarb) Phenyl carbamate compounds; 3-cyano-4- (2,2-difluoro-1 Cyanopyrrole compounds such as 3-benzodioxol-4-yl) pyrrole (generic name: fludioxonil), 3- (2 ′, 3′-dichlorophenyl) -4-cyano-pyrrole (generic name: fenpiclonyl) possible.

Examples Hereinafter, the compounds of the present invention will be specifically described with reference to Examples, Formulation Examples and Test Examples, but the present invention is not limited thereto.

Example 1
3,4-Dihydro-2H-1,3′-biquinolin-2-one (Compound No. 1) (Step A)
3,4-dihydroquinolin-2 (1H) -one (1.48 g, 10.1 mmol), 3-bromoquinoline (2.51 g, 12.1 mmol), copper iodide (206 mg, 1.08 mmol), potassium carbonate (1.40 g, 10.1) mmol) and N-methylpyrrolidone (2.00 g, 20.2 mmol) were stirred at 180 ° C. for 3 hours. After completion of the reaction, aqueous ammonia was poured and extracted with ethyl acetate. The combined organic layer was washed once with brine, dried over anhydrous sodium sulfate, and the solution was concentrated. The obtained residue was purified by silica gel column chromatography (hexane: ethyl acetate = 7: 3-6: 4-5: 5) to obtain 2.29 g (yield 83%) of the desired product.
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 2.90 (2H, dd, J = 8.5 Hz, 6.1 Hz), 3.14 (2H, dd, J = 8.5 Hz, 6.1 Hz), 6.36-6.42 (1H , m), 7.00-7.08 (2H, m), 7.24-7.28 (1H, m), 7.60 (1H, dd, J = 8.2Hz, 6.9Hz), 7.78 (1H, dd, J = 8.4Hz, 6.9Hz ), 7.83 (1H, d, J = 8.2Hz), 8.13 (1H, d, J = 2.4Hz), 8.18 (1H, d, J = 8.4Hz), 8.75 (1H, d, J = 2.4Hz).

Example 2
3,3-Dimethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 7) (Step B)
A THF solution (5 ml) of lithium = diisopropylamide (10 mmol) was prepared, and the compound of compound No. 1 (1.3 g, 4.7 mmol) obtained in Example 1 was added thereto, followed by stirring at 0 ° C. for 2 hours. The reaction solution was cooled to −78 ° C., methyl iodide (0.3 ml, 5.0 mmol) was added, and the reaction solution was allowed to warm to room temperature. After completion of the reaction, water was poured and extracted with ethyl acetate. The combined organic layer was washed once with brine, dried over anhydrous sodium sulfate, and the solution was concentrated. The obtained residue was purified by silica gel column chromatography (hexane: ethyl acetate = 7: 3) to obtain 450 mg of the desired product (yield 33%).
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.33 (6H, s), 3.00 (2H, s), 6.31-6.36 (1H, m), 7.02-7.05 (2H, m), 7.23-7.25 (1H, m), 7.60 (1H, dd, J = 8.4Hz, 7.2Hz), 7.78 (1H, dd, J = 8.4Hz, 7.2Hz), 7.83 (1H, d, J = 8.4Hz), 8.09 ( 1H, d, J = 2.4Hz), 8.18 (1H, d, J = 8.4Hz), 8.72 (1H, d, J = 2.4Hz).

Example 3
5,8-Difluoro-3,3,4,4-tetramethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 622) (Step A)

(3-1) N- (2,5-difluorophenyl) -2,2,3-trimethyl-3-butenylamide A solution of 2,5-difluoroaniline (510 mg, 3.95 mmol) in methylene chloride (5 ml) under ice-cooling Pyridine (0.38 ml, 4.74 mmol) and 2,2,3-trimethyl-3-butenoyl chloride (0.57 g, 3.95 mmol) were sequentially added, and the mixture was stirred at room temperature overnight. After completion of the reaction, saturated brine was poured and extracted with methylene chloride. The combined organic layer was washed once with brine, dried over anhydrous sodium sulfate, and the solution was concentrated. The obtained residue was purified by silica gel column chromatography (hexane: ethyl acetate = 95: 5) to obtain 713.4 mg (yield 75%) of the desired product.
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.41 (6H, s), 1.81 (3H, s), 5.15 (2H, d, J = 9.5 Hz), 6.64-6.73 (1H, m), 6.95-7.04 (1H, m), 7.80 (1H, brs), 8.12-8.19 (1H, m).

(3-2) 5,8-Difluoro-3,3,4,4-tetramethyl-3,4-dihydroquinolin-2 (1H) -one The anilide (669.1 mg, 2.80) obtained in the above 3-1 mmol) was heated to 120 ° C. to dissolve, and aluminum chloride (0.54 g, 4.19 mmol) was added to the solution at once and stirred for 2 hours. After completion of the reaction, dilute hydrochloric acid was poured and extracted with ethyl acetate. The combined organic layer was washed once with an aqueous sodium hydrogen carbonate solution and once with brine, dried over anhydrous sodium sulfate, and concentrated. The obtained residue was purified by silica gel column chromatography (hexane: ethyl acetate = 9: 1) to obtain 346.1 mg (yield 52%) of the desired product.
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.19 (6H, s), 1.37 (3H, s), 1.38 (3H, s), 6.59-6.69 (1H, m), 6.87-6.96 (1H , m), 7.57 (1H, brs).

(3-3) 5,8-Difluoro-3,3,4,4-tetramethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 622)
Quinolinone (92.2 mg, 0.385 mmol), 3-bromoquinoline (241 mg, 0.385 mmol), copper iodide (15 mg, 0.077 mmol), potassium carbonate (80 mg, 0.58 mmol) and N- A mixture of methylpyrrolidone (115 mg, 1.16 mmol) was stirred at 200 ° C. for 2 hours. After completion of the reaction, aqueous ammonia was poured and extracted with ethyl acetate. The combined organic layer was washed once with brine, dried over anhydrous sodium sulfate, and the solution was concentrated. The obtained residue was purified by silica gel column chromatography (hexane: ethyl acetate = 8: 2-7: 3) to obtain 97.1 mg (yield 69%) of the desired product.
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.21 (3H, s), 1.32 (3H, s), 1.39 (3H, s), 1.61 (3H, s), 6.79-6.85 (2H, m ), 7.54 (1H, dd, J = 8.2Hz, 7.1Hz), 7.71 (1H, dd, J = 8.2Hz, 7.1Hz), 7.76 (1H, d, J = 8.2Hz), 7.93 (1H, brs) , 8.13 (1H, d, J = 8.2Hz), 8.73 (1H, brs).

  The following compounds were synthesized in the same manner as in Examples 1 to 3.

Example 4
3-Methyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 2)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.38 (3H, d, J = 6.6 Hz), 2.86-3.14 (3H, m), 6.35-6.39 (1H, m), 7.00-7.07 (2H , m), 7.23-7.27 (1H, m), 7.59 (1H, dd, J = 7.9Hz, 6.9Hz), 7.77 (1H, dd, J = 8.4Hz, 6.9Hz), 7.83 (1H, d, J = 7.9Hz), 8.12 (1H, d, J = 2.4Hz), 8.17 (1H, d, J = 8.4Hz), 8.73 (1H, d, J = 2.4Hz).

Example 5
3-ethyl-3-methyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 8)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 0.98 (3H, d, J = 7.4 Hz), 1.30 (3H, s), 1.59-1.77 (2H, m), 3.00 (2H, s), 6.29-6.32 (1H, m), 7.01-7.04 (2H, m), 7.21-7.26 (1H, m), 7.59 (1H, dd, J = 7.9Hz, 6.9Hz), 7.77 (1H, dd, J = 8.4Hz, 6.9Hz), 7.83 (1H, d, J = 7.9Hz), 8.08 (1H, d, J = 2.4Hz), 8.18 (1H, d, J = 8.4Hz), 8.70 (1H, d, J = 2.4Hz).

Example 6
3-Methyl-3-propyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 9)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 0.91 (3H, t, J = 7.1 Hz), 1.31 (3H, s), 1.31-1.70 (4H, m), 3.00 (2H, s), 6.29-6.33 (1H, m), 7.00-7.04 (2H, m), 7.20-7.25 (1H, m), 7.59 (1H, dd, J = 8.2Hz, 6.9Hz), 7.77 (1H, ddd, J = 8.4Hz, 6.9Hz), 7.83 (1H, d, J = 8.2Hz), 8.08 (1H, d, J = 2.4Hz), 8.18 (1H, d, J = 8.4Hz), 8.70 (1H, d, J = 2.4Hz).

Example 7
3-Butyl-3-methyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 11)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 0.89 (3H, t, J = 7.1 Hz), 1.25-1.41 (4H, m), 1.31 (3H, s), 1.52-1.66 (2H, m ), 3.00 (2H, s), 6.29-6.33 (1H, m), 6.99-7.04 (2H, m), 7.20-7.25 (1H, m), 7.59 (1H, dd, J = 7.9Hz, 6.9Hz) , 7.77 (1H, dd, J = 8.4Hz, 6.9Hz), 7.83 (1H, d, J = 7.9Hz), 8.08 (1H, d, J = 2.4Hz), 8.17 (1H, d, J = 8.4Hz ), 8.70 (1H, d, J = 2.4Hz).

Example 8
3,3,4,4-tetramethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 39)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.26 (6H, brs), 1.40 (6H, brs), 6.36 (1H, dd, J = 7.4 Hz, 1.6 Hz), 7.02 (1H, td, J = 7.4Hz, 1.6Hz), 7.08 (1H, td, J = 7.4Hz, 1.6Hz), 7.37 (1H, dd, J = 7.4Hz, 1.6Hz), 7.58 (1H, dd, J = 8.2Hz, 7.0Hz), 7.72 (1H, dd, J = 8.2Hz, 7.0Hz), 7.82 (1H, d, J = 8.2Hz), 8.08 (1H, d, J = 2.1Hz), 8.17 (1H, d, J = 8.2Hz), 8.70 (1H, d, J = 2.1Hz).

Example 9
5-Fluoro-3-methyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 55)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.41 (3H, d, J = 6.6 Hz), 2.77-2.95 (2H, m), 3.30 (1H, dd, J = 14.0 Hz, 3.4 Hz) , 6.15 (1H, d, J = 8.2Hz), 6.80 (1H, t, J = 8.2Hz), 7.00 (1H, td, J = 8.2Hz, 6.0Hz), 7.60 (1H, dd, J = 8.2Hz , 7.1Hz), 7.78 (1H, dd, J = 8.2Hz, 7.1Hz), 7.83 (1H, d, J = 8.2Hz), 8.10 (1H, d, J = 2.4Hz), 8.18 (1H, d, J = 8.2Hz), 8.71 (1H, d, J = 2.4Hz).

Example 10
5-Fluoro-3-phenyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 59)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 3.50 (2H, d, J = 7.1 Hz), 4.14 (1H, t, J = 7.1 Hz), 6.18 (1H, d, J = 8.4 Hz) , 6.82 (1H, t, J = 8.4Hz), 7.01 (1H, td, J = 8.4Hz, 6.1Hz), 7.28-7.39 (5H, m), 7.61 (1H, dd, J = 8.0Hz, 7.1Hz ), 7.78 (1H, dd, J = 8.4Hz, 7.1Hz), 7.83 (1H, d, J = 8.0Hz), 8.13 (1H, d, J = 2.1Hz), 8.17 (1H, d, J = 8.4 Hz), 8.74 (1H, d, J = 2.1Hz).

Example 11
5-Fluoro-3,3-dimethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 60)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.35 (6H, s), 3.01 (2H, s), 6.11 (1H, d, J = 8.4 Hz), 6.80 (1H, t, J = 8.4 Hz), 6.99 (1H, td, J = 8.4Hz, 6.1Hz), 7.59 (1H, dd, J = 8.4Hz, 6.9Hz), 7.78 (1H, dd, J = 8.4Hz, 6.9Hz), 7.83 ( 1H, d, J = 8.4Hz), 8.08 (1H, d, J = 2.4Hz), 8.18 (1H, d, J = 8.4Hz), 8.69 (1H, d, J = 2.4Hz).

Example 12
3-ethyl-5-fluoro-3-methyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 61)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.00 (3H, t, J = 7.4 Hz), 1.33 (3H, s), 1.66 (1H, dd, J = 13.8 Hz, 7.4 Hz), 1.74 (1H, dd, J = 13.8Hz, 7.4Hz), 2.93 (1H, d, J = 16.3Hz), 3.12 (1H, d, J = 16.3Hz), 6.10 (1H, d, J = 8.4Hz), 6.79 (1H, t, J = 8.4Hz), 6.98 (1H, td, J = 8.4Hz, 6.0Hz), 7.59 (1H, dd, J = 8.2Hz, 6.9Hz), 7.78 (1H, dd, J = 8.4Hz, 6.9Hz), 7.83 (1H, d, J = 8.2Hz), 8.07 (1H, d, J = 2.4Hz), 8.18 (1H, d, J = 8.4Hz), 8.68 (1H, d, J = 2.4Hz).

Example 13
5-Fluoro-3-methyl-3-propyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 62)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 0.93 (3H, t, J = 7.1 Hz), 1.34 (3H, s), 1.37-1.69 (4H, m), 2.93 (1H, d, J = 16.1Hz), 3.12 (1H, d, J = 16.1Hz), 6.10 (1H, d, J = 8.2Hz), 6.80 (1H, t, J = 8.2Hz), 6.99 (1H, td, J = 8.2 Hz, 6.1Hz), 7.60 (1H, dd, J = 8.2Hz, 6.9Hz), 7.78 (1H, dd, J = 8.2Hz, 6.9Hz), 7.83 (1H, d, J = 8.2Hz), 8.06 ( 1H, d, J = 2.1Hz), 8.17 (1H, d, J = 8.2Hz), 8.67 (1H, d, J = 2.1Hz).

Example 14
3-Butyl-5-fluoro-3-methyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 64)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 0.90 (3H, t, J = 7.0 Hz), 1.23-1.45 (4H, m), 1.34 (3H, s), 1.54-1.70 (2H, m ), 2.93 (1H, d, J = 16.1Hz), 3.12 (1H, d, J = 16.1Hz), 6.10 (1H, d, J = 8.2Hz), 6.80 (1H, t, J = 8.2Hz), 7.00 (1H, td, J = 8.2Hz, 6.1Hz), 7.59 (1H, dd, J = 8.2Hz, 6.9Hz), 7.78 (1H, dd, J = 8.4Hz, 6.9Hz), 7.83 (1H, d , J = 8.2Hz), 8.07 (1H, d, J = 2.4Hz), 8.18 (1H, d, J = 8.4Hz), 8.68 (1H, d, J = 2.4Hz).

Example 15
5-Fluoro-3-methyl-3-phenyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 69)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.68 (3H, s), 3.16 (1H, d, J = 16.6 Hz), 3.89 (1H, d, J = 16.6 Hz), 5.96 (1H, d, J = 8.4Hz), 6.73 (1H, t, J = 8.4Hz), 6.86 (1H, td, J = 8.2Hz, 6.6Hz), 7.18-7.34 (3H, m), 7.40 (2H, dd, J = 7.4Hz, 1.3Hz), 7.60 (1H, dd, J = 8.0Hz, 6.8Hz), 7.78 (1H, dd, J = 8.4Hz, 6.8Hz), 7.84 (1H, d, J = 8.0Hz) , 8.06 (1H, d, J = 2.4Hz), 8.17 (1H, d, J = 8.4Hz), 8.67 (1H, d, J = 2.4Hz).

Example 16
5-Fluoro-3-hydroxy-3-methyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 70)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.49 (3H, s), 3.14 (1H, d, J = 16.0 Hz), 3.44 (1H, d, J = 16.0 Hz), 3.89 (1H, s), 6.19 (1H, d, J = 8.2Hz), 6.86 (1H, dd, J = 8.2Hz, 7.7Hz), 7.04 (1H, dd, J = 14.5Hz, 8.2Hz), 7.63 (1H, dd , J = 8.2Hz, 6.9Hz), 7.82 (1H, dd, J = 8.2Hz, 6.9Hz), 7.86 (1H, d, J = 8.2Hz), 8.12 (1H, d, J = 2.4Hz), 8.20 (1H, d, J = 8.2Hz), 8.72 (1H, d, J = 2.4Hz).

Example 17
Ethyl 5-fluoro-3-methyl-2-oxo-3,4-dihydro-2H-1,3′-biquinoline-3-carboxylate (Compound No. 76)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.14 (3H, t, J = 7.1 Hz), 1.67 (3H, s), 2.96 (1H, d, J = 16.0 Hz), 3.75 (1H, d, J = 16.0Hz), 4.08-4.21 (2H, m), 6.13 (1H, d, J = 8.2Hz), 6.80 (1H, t, J = 8.2Hz), 7.00 (1H, td, J = 8.2 Hz, 6.0Hz), 7.61 (1H, dd, J = 8.4Hz, 6.9Hz), 7.80 (1H, dd, J = 8.4Hz, 6.9Hz), 7.83 (1H, d, J = 8.4Hz), 8.14 ( 1H, d, J = 1.8Hz), 8.20 (1H, d, J = 8.4Hz), 8.75 (1H, d, J = 1.8Hz).

Example 18
Ethyl 5-fluoro-2-oxo-3-phenyl-3,4-dihydro-2H-1,3′-biquinoline-3-carboxylate (Compound No. 85)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.16 (3H, t, J = 7.1 Hz), 3.79 (1H, d, J = 16.0 Hz), 4.04 (1H, d, J = 16.0 Hz) , 4.21 (2H, q, J = 7.1Hz), 6.11 (1H, d, J = 8.2Hz), 6.80 (1H, t, J = 8.2Hz), 6.98 (1H, td, J = 8.2Hz, 6.1Hz ), 7.31-7.48 (5H, m), 7.61 (1H, dd, J = 8.2Hz, 7.1Hz), 7.79 (1H, dd, J = 8.2Hz, 7.1Hz), 7.85 (1H, d, J = 8.2 Hz), 8.16 (1H, d, J = 2.4Hz), 8.17 (1H, d, J = 8.2Hz), 8.76 (1H, d, J = 2.4Hz).

Example 19
5-Fluoro-4,4-dimethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 88)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.58 (6H, d, J = 2.9 Hz), 2.76 (2H, s), 6.20 (1H, d, J = 8.2 Hz), 6.78 (1H, dd, J = 11.4Hz, 8.2Hz), 6.98 (1H, td, J = 8.2Hz, 5.8Hz), 7.60 (1H, dd, J = 7.9Hz, 6.9Hz), 7.78 (1H, dd, J = 8.4 Hz, 6.9Hz), 7.84 (1H, d, J = 7.9Hz), 8.08 (1H, d, J = 2.4Hz), 8.18 (1H, d, J = 8.4Hz), 8.68 (1H, d, J = 2.4Hz).

Example 20
5-Fluoro-3,4,4-trimethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 89)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.28 (3H, d, J = 7.2 Hz), 1.53 (6H, s), 2.60 (1H, q, J = 7.2 Hz), 6.19 (1H, d, J = 8.2Hz), 6.78 (1H, dd, J = 11.6Hz, 8.2Hz), 6.97 (1H, td, J = 8.2Hz, 5.6Hz), 7.60 (1H, dd, J = 7.9Hz, 6.9 Hz), 7.78 (1H, dd, J = 8.4Hz, 6.9Hz), 7.83 (1H, d, J = 7.9Hz), 8.05 (1H, d, J = 2.4Hz), 8.17 (1H, d, J = 8.4Hz), 8.65 (1H, d, J = 2.4Hz).

Example 21
5-Fluoro-3,3,4,4-tetramethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 92)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.30 (6H, s), 1.53 (6H, brs), 6.14 (1H, d, J = 8.2 Hz), 6.76 (1H, dd, J = 11.6 Hz, 8.2Hz), 6.95 (1H, td, J = 8.2Hz, 5.8Hz), 7.59 (1H, dd, J = 7.9Hz, 7.1Hz), 7.78 (1H, dd, J = 8.4Hz, 7.1Hz) , 7.82 (1H, d, J = 7.9Hz), 8.04 (1H, brs), 8.18 (1H, d, J = 8.4Hz), 8.64 (1H, brs).

Example 22
6-Fluoro-3-methyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 108)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.38 (3H, d, J = 6.4 Hz), 2.85-3.13 (3H, m), 6.33 (1H, dd, J = 8.5 Hz, 4.5 Hz) , 6.75 (1H, td, J = 8.5Hz, 2.9Hz), 6.98 (1H, dd, J = 8.5Hz, 2.9Hz), 7.60 (1H, dd, J = 8.4Hz, 6.9Hz), 7.78 (1H, dd, J = 8.4Hz, 6.9Hz), 7.83 (1H, d, J = 8.4Hz), 8.11 (1H, d, J = 2.4Hz), 8.17 (1H, d, J = 8.4Hz), 8.72 (1H , d, J = 2.4Hz).

Example 23
6-Fluoro-3,3-dimethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 113)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.32 (6H, s), 2.97 (2H, s), 6.28 (1H, dd, J = 8.5 Hz, 4.5 Hz), 6.73 (1H, td, J = 8.5Hz, 2.6Hz), 6.96 (1H, dd, J = 8.5Hz, 2.6Hz), 7.59 (1H, dd, J = 8.2Hz, 6.9Hz), 7.78 (1H, dd, J = 8.2Hz, 6.9Hz), 7.83 (1H, d, J = 8.2Hz), 8.09 (1H, d, J = 2.1Hz), 8.17 (1H, d, J = 8.2Hz), 8.69 (1H, d, J = 2.1Hz ).

Example 24
3-ethyl-6-fluoro-3-methyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 114)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 0.98 (3H, t, J = 7.4 Hz), 1.29 (3H, s), 1.58-1.76 (2H, m), 2.97 (2H, s), 6.27 (1H, dd, J = 8.5Hz, 4.5Hz), 6.72 (1H, td, J = 8.5Hz, 2.9Hz), 6.96 (1H, dd, J = 8.5Hz, 2.9Hz), 7.59 (1H, dd , J = 8.2Hz, 6.9Hz), 7.77 (1H, dd, J = 8.2Hz, 6.9Hz), 7.83 (1H, d, J = 8.2Hz), 8.08 (1H, d, J = 2.4Hz), 8.17 (1H, d, J = 8.2Hz), 8.68 (1H, d, J = 2.4Hz).

Example 25
6-Fluoro-3-methyl-3-propyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 115)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 0.92 (3H, t, J = 7.1 Hz), 1.31 (3H, s), 1.33-1.63 (4H, m), 2.98 (2H, s), 6.27 (1H, dd, J = 8.7Hz, 4.8Hz), 6.73 (1H, td, J = 8.7Hz, 2.9Hz), 6.96 (1H, dd, J = 8.7Hz, 2.9Hz), 7.59 (1H, dd , J = 8.4Hz, 7.1Hz), 7.77 (1H, dd, J = 8.4Hz, 7.1Hz), 7.83 (1H, d, J = 8.4Hz), 8.08 (1H, d, J = 2.4Hz), 8.17 (1H, d, J = 8.4Hz), 8.68 (1H, d, J = 2.4Hz).

Example 26
3-Butyl-6-fluoro-3-methyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 117)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 0.90 (3H, t, J = 6.9 Hz), 1.22-1.40 (4H, m), 1.30 (3H, s), 1.51-1.68 (2H, m ), 2.98 (2H, s), 6.27 (1H, dd, J = 8.4Hz, 4.8Hz), 6.73 (1H, td, J = 8.4Hz, 2.6Hz), 6.97 (1H, dd, J = 8.4Hz, 2.6Hz), 7.59 (1H, dd, J = 8.2Hz, 7.1Hz), 7.77 (1H, dd, J = 8.2Hz, 7.1Hz), 7.83 (1H, d, J = 8.2Hz), 8.08 (1H, d, J = 2.4Hz), 8.17 (1H, d, J = 8.2Hz), 8.68 (1H, d, J = 2.4Hz).

Example 27
Ethyl 6-fluoro-3-methyl-2-oxo-3,4-dihydro-2H-1,3′-biquinoline-3-carboxylate (Compound No. 129)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.13 (3H, t, J = 7.1 Hz), 1.64 (3H, s), 3.15 (1H, d, J = 15.8 Hz), 3.43 (1H, d, J = 15.8Hz), 4.03-4.23 (2H, m), 6.30 (1H, dd, J = 8.8Hz, 4.5Hz), 6.75 (1H, td, J = 8.8Hz, 2.6Hz), 6.99 (1H , dd, J = 8.2Hz, 2.6Hz), 7.61 (1H, dd, J = 8.4Hz, 6.9Hz), 7.80 (1H, dd, J = 8.4Hz, 6.9Hz), 7.84 (1H, d, J = 8.4Hz), 8.14 (1H, d, J = 2.4Hz), 8.18 (1H, d, J = 8.4Hz), 8.75 (1H, d, J = 2.4Hz).

Example 28
6-Fluoro-4,4-dimethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 141)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.47 (6H, s), 2.74 (2H, s), 6.39 (1H, dd, J = 9.0 Hz, 4.7 Hz), 6.75 (1H, td, J = 9.0Hz, 2.8Hz), 6.82 (1H, dd, J = 9.0Hz, 2.8Hz), 7.61 (1H, dd, J = 8.4Hz, 7.2Hz), 7.78 (1H, dd, J = 8.4Hz, 7.2Hz), 7.85 (1H, d, J = 8.4Hz), 8.11 (1H, d, J = 2.4Hz), 8.17 (1H, d, J = 8.4Hz), 8.72 (1H, d, J = 2.4Hz ).

Example 29
6-Fluoro-3,4,4-trimethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 142)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.23 (3H, d, J = 7.1 Hz), 1.36 (3H, s), 1.45 (3H, s), 2.60 (1H, q, J = 7.1 Hz), 6.38 (1H, dd, J = 9.0Hz, 5.0Hz), 6.75 (1H, td, J = 9.0Hz, 2.9Hz), 7.09 (1H, dd, J = 9.0Hz, 2.9Hz), 7.60 ( 1H, dd, J = 8.2Hz, 6.9Hz), 7.78 (1H, dd, J = 8.2Hz, 6.9Hz), 7.83 (1H, d, J = 8.2Hz), 8.08 (1H, d, J = 2.4Hz ), 8.17 (1H, d, J = 8.2Hz), 8.69 (1H, d, J = 2.4Hz).

Example 30
6-Fluoro-3,3,4,4-tetramethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 145)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.25 (6H, brs), 1.39 (6H, brs), 6.33 (1H, dd, J = 8.7Hz, 5.0Hz), 6.72 (1H, td, J = 8.7Hz, 2.9Hz), 7.09 (1H, dd, J = 8.7Hz, 2.9Hz), 7.59 (1H, dd, J = 7.9Hz, 7.1Hz), 7.77 (1H, dd, J = 8.4Hz, 7.1Hz), 7.82 (1H, d, J = 7.9Hz), 8.07 (1H, d, J = 2.4Hz), 8.17 (1H, d, J = 8.4Hz), 8.68 (1H, d, J = 2.4Hz ).

Example 31
7-Fluoro-3-methyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 161)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.38 (3H, d, J = 6.3 Hz), 2.85-3.16 (3H, m), 6.09 (1H, dd, J = 10.3 Hz, 2.4 Hz) , 6.72 (1H, td, J = 8.2Hz, 2.4Hz), 7.20 (1H, dd, J = 8.2Hz, 6.1Hz), 7.61 (1H, dd, J = 8.2Hz, 6.9Hz), 7.80 (1H, dd, J = 8.4Hz, 6.9Hz), 7.84 (1H, d, J = 8.2Hz), 8.10 (1H, d, J = 2.4Hz), 8.19 (1H, d, J = 8.4Hz), 8.72 (1H , d, J = 2.4Hz).

Example 32
7-Fluoro-3,3-dimethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 166)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.32 (6H, s), 2.95 (2H, s), 6.05 (1H, dd, J = 10.3 Hz, 2.4 Hz), 6.72 (1H, td, J = 8.2Hz, 2.4Hz), 7.18 (1H, dd, J = 8.2Hz, 6.0Hz), 7.61 (1H, dd, J = 8.2Hz, 7.1Hz), 7.79 (1H, dd, J = 8.2Hz, 7.1Hz), 7.84 (1H, d, J = 8.2Hz), 8.08 (1H, d, J = 2.4Hz), 8.19 (1H, d, J = 8.2Hz), 8.69 (1H, d, J = 2.4Hz ).

Example 33
3-ethyl-7-fluoro-3-methyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 167)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 0.98 (3H, t, J = 7.4 Hz), 1.29 (3H, s), 1.57-1.77 (2H, m), 2.96 (2H, s), 6.03 (1H, dd, J = 10.3Hz, 2.4Hz), 6.71 (1H, td, J = 8.2Hz, 2.4Hz), 7.17 (1H, dd, J = 8.2Hz, 6.3Hz), 7.61 (1H, dd , J = 8.4Hz, 6.9Hz), 7.79 (1H, dd, J = 8.4Hz, 6.9Hz), 7.84 (1H, d, J = 8.4Hz), 8.07 (1H, d, J = 2.4Hz), 8.19 (1H, d, J = 8.4Hz), 8.68 (1H, d, J = 2.4Hz).

Example 34
7-Fluoro-3-methyl-3-propyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 168)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 0.92 (3H, t, J = 7.1 Hz), 1.31 (3H, s), 1.31-1.67 (4H, m), 2.96 (2H, s), 6.04 (1H, dd, J = 10.3Hz, 2.4Hz), 6.71 (1H, td, J = 8.1Hz, 2.4Hz), 7.17 (1H, dd, J = 8.1Hz, 6.1Hz), 7.61 (1H, dd , J = 8.2Hz, 6.9Hz), 7.79 (1H, dd, J = 8.2Hz, 6.9Hz), 7.84 (1H, d, J = 8.2Hz), 8.07 (1H, d, J = 2.4Hz), 8.19 (1H, d, J = 8.2Hz), 8.68 (1H, d, J = 2.4Hz).

Example 35
3-Butyl-7-fluoro-3-methyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 170)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 0.90 (3H, t, J = 7.0 Hz), 1.22-1.43 (4H, m), 1.30 (3H, s), 1.51-1.68 (2H, m ), 2.96 (2H, s), 6.04 (1H, dd, J = 10.3Hz, 2.4Hz), 6.71 (1H, td, J = 8.2Hz, 2.4Hz), 7.16 (1H, dd, J = 8.2Hz, 6.0Hz), 7.60 (1H, dd, J = 8.0Hz, 6.9Hz), 7.79 (1H, dd, J = 8.4Hz, 6.9Hz), 7.84 (1H, d, J = 8.0Hz), 8.07 (1H, d, J = 2.4Hz), 8.19 (1H, d, J = 8.4Hz), 8.68 (1H, d, J = 2.4Hz).

Example 36
Ethyl 7-fluoro-3-methyl-2-oxo-3,4-dihydro-2H-1,3′-biquinoline-3-carboxylate (Compound No. 182)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.13 (3H, t, J = 7.1 Hz), 1.64 (3H, s), 3.12 (1H, d, J = 15.6 Hz), 3.43 (1H, d, J = 15.6Hz), 4.05-4.20 (2H, m), 6.06 (1H, dd, J = 10.0Hz, 2.4Hz), 6.72 (1H, td, J = 8.2Hz, 2.4Hz), 7.20 (1H , dd, J = 8.2Hz, 5.8Hz), 7.59-7.65 (1H, m), 7.77-7.87 (2H, m), 8.13 (1H, d, J = 2.1Hz), 8.20 (1H, d, J = 8.4Hz), 8.76 (1H, d, J = 2.1Hz).

Example 37
7-Fluoro-4,4-dimethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 194)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.46 (6H, s), 2.75 (2H, s), 6.14 (1H, dd, J = 10.3 Hz, 2.6 Hz), 6.78 (1H, td, J = 8.4Hz, 2.6Hz), 7.33 (1H, dd, J = 8.4Hz, 6.0Hz), 7.62 (1H, dd, J = 7.9Hz, 6.9Hz), 7.80 (1H, dd, J = 8.4Hz, 6.9Hz), 7.85 (1H, d, J = 7.9Hz), 8.11 (1H, d, J = 2.4Hz), 8.19 (1H, d, J = 8.4Hz), 8.72 (1H, d, J = 2.4Hz ).

Example 38
7-Fluoro-3,4,4-trimethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 195)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.23 (3H, d, J = 7.1 Hz), 1.36 (3H, s), 1.44 (3H, s), 2.68 (1H, q, J = 7.1 Hz), 6.13 (1H, dd, J = 10.3Hz, 2.4Hz), 6.78 (1H, td, J = 8.4Hz, 2.4Hz), 7.31 (1H, dd, J = 8.4Hz, 6.1Hz), 7.60 ( 1H, dd, J = 8.0Hz, 6.9Hz), 7.79 (1H, dd, J = 8.4Hz, 6.9Hz), 7.84 (1H, d, J = 8.0Hz), 8.08 (1H, d, J = 2.4Hz ), 8.19 (1H, d, J = 8.4Hz), 8.69 (1H, d, J = 2.4Hz).

Example 39
7-Fluoro-3,3,4,4-tetramethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 198)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.25 (6H, brs), 1.38 (6H, brs), 6.06 (1H, dd, J = 10.3Hz, 2.4Hz), 6.76 (1H, td, J = 8.4Hz, 2.4Hz), 7.31 (1H, dd, J = 8.4Hz, 6.1Hz), 7.61 (1H, dd, J = 8.4Hz, 6.9Hz), 7.82 (1H, dd, J = 7.9Hz, 7.1Hz), 7.84 (1H, d, J = 7.9Hz), 8.07 (1H, brs), 8.19 (1H, d, J = 8.4Hz), 8.68 (1H, brs).

Example 40
8-Fluoro-4,4-dimethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 247)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.46 (6H, s), 2.70 (2H, s), 6.39 (1H, dd, J = 12.4Hz, 7.9Hz), 7.13 (1H, td, J = 7.9Hz, 4.7Hz), 7.20 (1H, d, J = 7.9Hz), 7.55 (1H, dd, J = 8.2Hz, 7.1Hz), 7.71 (1H, dd, J = 8.2Hz, 7.1Hz) , 7.79 (1H, d, J = 8.2Hz), 8.01 (1H, d, J = 2.4Hz), 8.13 (1H, d, J = 8.2Hz), 8.81 (1H, d, J = 2.4Hz).

Example 41
8-Fluoro-3,4,4-trimethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 248)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.21 (3H, d, J = 7.1 Hz), 1.33 (3H, s), 1.45 (3H, s), 2.67 (1H, q, J = 7.1 Hz), 6.89 (1H, ddd, J = 11.5Hz, 7.9Hz, 1.5Hz), 7.13 (1H, td, J = 7.9Hz, 4.5Hz), 7.19 (1H, dd, J = 7.9Hz, 1.5Hz) , 7.55 (1H, dd, J = 7.9Hz, 7.1Hz), 7.71 (1H, dd, J = 8.4Hz, 7.1Hz), 7.78 (1H, d, J = 7.9Hz), 8.00 (1H, d, J = 2.1Hz), 8.13 (1H, d, J = 8.4Hz), 8.80 (1H, d, J = 2.1Hz).

Example 42
8-Fluoro-3,3,4,4-tetramethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 251)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.08 (3H, s), 1.32 (3H, s), 1.33 (3H, s), 1.44 (3H, s), 6.88 (1H, ddd, J = 11.6Hz, 7.9Hz, 1.6Hz), 7.12 (1H, td, J = 7.9Hz, 4.5Hz), 7.18 (1H, dd, J = 7.9Hz, 1.6Hz), 7.53 (1H, dd, J = 8.2 Hz, 6.9Hz), 7.71 (1H, dd, J = 8.4Hz, 6.9Hz), 7.77 (1H, d, J = 8.2Hz), 8.00 (1H, brs), 8.13 (1H, d, J = 8.4Hz ), 8.79 (1H, brs).

Example 43
5-Chloro-3-methyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 267)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.41 (3H, d, J = 6.3 Hz), 2.85-2.99 (2H, m), 3.36-3.49 (1H, m), 6.28 (1H, dd , J = 8.2Hz, 0.8Hz), 6.97 (1H, t, J = 8.2Hz), 7.11 (1H, dd, J = 8.2Hz, 0.8Hz), 7.60 (1H, dd, J = 8.0Hz, 6.9Hz ), 7.79 (1H, dd, J = 8.4Hz, 6.9Hz), 7.83 (1H, d, J = 8.0Hz), 8.09 (1H, d, J = 2.1Hz), 8.18 (1H, d, J = 8.4 Hz), 8.70 (1H, d, J = 2.1Hz).

Example 44
5-Chloro-3,3-dimethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 272)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.35 (6H, s), 3.13 (2H, s), 6.23 (1H, dd, J = 8.0 Hz, 1.0 Hz), 6.97 (1H, t, J = 8.0Hz), 7.11 (1H, dd, J = 8.0Hz, 1.0Hz), 7.60 (1H, dd, J = 8.2Hz, 6.9Hz), 7.79 (1H, dd, J = 8.4Hz, 6.9Hz) , 7.83 (1H, d, J = 8.2Hz), 8.07 (1H, d, J = 2.4Hz), 8.18 (1H, d, J = 8.4Hz), 8.67 (1H, d, J = 2.4Hz).

Example 45
5-Chloro-3-ethyl-3-methyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 273)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 0.99 (3H, t, J = 7.2 Hz), 1.33 (3H, s), 1.56-1.78 (2H, m), 3.02 (1H, d, J = 16.4Hz), 3.26 (1H, d, J = 16.4Hz), 6.22 (1H, d, J = 7.9Hz), 6.95 (1H, t, J = 7.9Hz), 7.10 (1H, d, J = 7.9 Hz), 7.59 (1H, dd, J = 8.2Hz, 6.9Hz), 7.78 (1H, dd, J = 8.4Hz, 6.9Hz), 7.83 (1H, d, J = 8.2Hz), 8.06 (1H, d , J = 2.4Hz), 8.18 (1H, d, J = 8.4Hz), 8.67 (1H, d, J = 2.4Hz).

Example 46
5-Chloro-3-methyl-3-propyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 274)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 0.92 (3H, t, J = 7.2 Hz), 1.34 (3H, s), 1.39-1.68 (4H, m), 3.02 (1H, d, J = 16.4Hz), 3.26 (1H, d, J = 16.4Hz), 6.22 (1H, d, J = 7.9Hz), 6.95 (1H, t, J = 7.9Hz), 7.10 (1H, d, J = 7.9 Hz), 7.58 (1H, dd, J = 8.2Hz, 6.9Hz), 7.77 (1H, dd, J = 8.2Hz, 6.9Hz), 7.83 (1H, d, J = 8.2Hz), 8.06 (1H, d , J = 2.4Hz), 8.17 (1H, d, J = 8.2Hz), 8.67 (1H, d, J = 2.4Hz).

Example 47
5-Chloro-3-butyl-3-methyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 276)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 0.90 (3H, t, J = 7.2 Hz), 1.14-1.43 (4H, m), 1.34 (3H, s), 1.56-1.68 (2H, m ), 3.03 (1H, d, J = 16.4Hz), 3.25 (1H, d, J = 16.4Hz), 6.22 (1H, d, J = 7.9Hz), 6.96 (1H, t, J = 7.9Hz), 7.10 (1H, d, J = 7.9Hz), 7.59 (1H, dd, J = 7.9Hz, 7.1Hz), 7.78 (1H, dd, J = 8.2Hz, 7.1Hz), 7.83 (1H, d, J = 7.9Hz), 8.06 (1H, d, J = 2.4Hz), 8.17 (1H, d, J = 8.2Hz), 8.67 (1H, d, J = 2.4Hz).

Example 48
Ethyl 5-chloro-3-methyl-2-oxo-3,4-dihydro-2H-1,3′-biquinoline-3-carboxylate (Compound No. 288)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.11 (3H, t, J = 7.1 Hz), 1.68 (3H, s), 3.04 (1H, d, J = 16.1 Hz), 3.90 (1H, d, J = 16.1Hz), 4.08-4.19 (2H, m), 6.26 (1H, d, J = 8.1Hz), 6.98 (1H, t, J = 8.1Hz), 7.11 (1H, d, J = 8.1 Hz), 7.61 (1H, dd, J = 7.9Hz, 6.9Hz), 7.79 (1H, dd, J = 8.4Hz, 6.9Hz), 7.84 (1H, d, J = 7.9Hz), 8.13 (1H, d , J = 2.1Hz), 8.18 (1H, d, J = 8.4Hz), 8.74 (1H, d, J = 2.1Hz).

Example 49
8-chloro-3,3,4,4-tetramethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 410)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.03 (3H, s), 1.29 (3H, s), 1.32 (3H, s), 1.43 (3H, s), 7.11-7.22 (2H, m ), 7.32 (1H, dd, J = 7.1Hz, 1.9Hz), 7.51 (1H, t, J = 7.4Hz), 7.65-7.72 (3H, m), 8.11 (1H, d, J = 8.2Hz), 8.92 (1H, brs).

Example 50
5,7-Difluoro-4,4-dimethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 565)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.56 (6H, d, J = 3.0 Hz), 2.72 (2H, s), 5.95 (1H, dd, J = 10.0 Hz, 2.4 Hz), 6.53 (1H, ddd, J = 11.4Hz, 8.4Hz, 2.4Hz), 7.62 (1H, dd, J = 7.9Hz, 7.1Hz), 7.80 (1H, dd, J = 8.4Hz, 7.1Hz), 7.85 (1H , d, J = 7.9Hz), 8.07 (1H, d, J = 2.4Hz), 8.19 (1H, d, J = 8.4Hz), 8.67 (1H, d, J = 2.4Hz).

Example 51
5,8-Difluoro-4,4-dimethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 618)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.56 (6H, d, J = 3.0 Hz), 2.73 (2H, s), 6.79-6.87 (2H, m), 7.55 (1H, dd, J = 8.2Hz, 6.9Hz), 7.72 (1H, dd, J = 8.4Hz, 6.9Hz), 7.78 (1H, d, J = 8.4Hz), 7.97 (1H, d, J = 2.4Hz), 8.13 (1H , d, J = 8.2Hz), 8.76 (1H, d, J = 2.4Hz).

Example 52
5,8-Difluoro-3,4,4-trimethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 619)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.25 (3H, d, J = 7.1 Hz), 1.49 (3H, d, J = 5.0 Hz), 1.53 (3H, d, J = 1.6 Hz) , 2.63 (1H, q, J = 7.1Hz), 6.79-6.87 (2H, m), 7.55 (1H, dd, J = 7.9Hz, 6.9Hz), 7.72 (1H, dd, J = 8.4Hz, 6.9Hz ), 7.78 (1H, dd, J = 7.9Hz), 7.95 (1H, d, J = 2.1Hz), 8.13 (1H, d, J = 8.4Hz), 8.74 (1H, d, J = 2.1Hz).

Example 53
8-chloro-5-fluoro-3,3,4,4-tetramethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 675)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.16 (3H, s), 1.31 (3H, s), 1.35 (3H, s), 1.61 (3H, d, J = 6.8 Hz), 6.88 ( 1H, dd, J = 11.4Hz, 9.0Hz), 7.14 (1H, dd, J = 9.0Hz, 5.0Hz), 7.52 (1H, dd, J = 8.2Hz, 7.2Hz), 7.66-7.75 (3H, m ), 8.10 (1H, d, J = 8.2Hz), 8.92 (1H, brs).

Example 54
4,4,5-Trimethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 724)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.58 (6H, s), 2.57 (3H, s), 2.74 (2H, s), 6.31 (1H, dd, J = 7.4 Hz, 1.8 Hz) , 6.87 (1H, dd, J = 7.4Hz, 1.8Hz), 6.90 (1H, t, J = 7.4Hz), 7.59 (1H, dd, J = 7.9Hz, 7.1Hz), 7.76 (1H, dd, J = 8.4Hz, 7.1Hz), 7.82 (1H, d, J = 7.9Hz), 8.08 (1H, d, J = 2.1Hz), 8.17 (1H, d, J = 8.4Hz), 8.66 (1H, d, J = 2.1Hz).

Example 55
3,4,4,5-tetramethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 725)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.24 (3H, d, J = 7.1 Hz), 1.50 (3H, s), 1.57 (3H, s), 2.50 (1H, q, J = 7.1 Hz), 2.54 (3H, s), 6.28 (1H, dd, J = 7.1Hz, 1.1Hz), 6.84 (1H, dd, J = 7.1Hz, 1.1Hz), 7.17 (1H, t, J = 7.1Hz ), 7.56 (1H, dd, J = 8.2Hz, 7.0Hz), 7.74 (1H, dd, J = 8.2Hz, 7.0Hz), 7.80 (1H, d, J = 8.2Hz), 8.08 (1H, d, J = 1.8Hz), 8.17 (1H, d, J = 8.2Hz), 8.70 (1H, d, J = 1.8Hz).

Example 56
4,4,6-Trimethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 777)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.46 (6H, s), 2.33 (3H, s), 2.73 (2H, s), 6.32 (1H, d, J = 8.2 Hz), 6.84 ( 1H, d, J = 8.2Hz), 7.19 (1H, s), 7.59 (1H, dd, J = 7.9Hz, 6.9Hz), 7.77 (1H, dd, J = 8.4Hz, 6.9Hz), 7.83 (1H , d, J = 7.9Hz), 8.10 (1H, d, J = 2.1Hz), 8.17 (1H, d, J = 8.4Hz), 8.72 (1H, d, J = 2.1Hz).

Example 57
3,4,4,6-tetramethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 778)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.22 (3H, d, J = 7.1 Hz), 1.36 (3H, s), 1.44 (3H, s), 2.33 (3H, s), 2.66 ( 1H, q, J = 7.1Hz), 6.31 (1H, d, J = 8.2Hz), 6.85 (1H, dd, J = 8.2Hz, 1.1Hz), 7.17 (1H, d, J = 1.1Hz), 7.58 (1H, dd, J = 7.9Hz, 6.9Hz), 7.76 (1H, dd, J = 8.4Hz, 6.9Hz), 7.82 (1H, d, J = 7.9Hz), 8.08 (1H, d, J = 2.1 Hz), 8.17 (1H, d, J = 8.4Hz), 8.70 (1H, d, J = 2.1Hz).

Example 58
3,3,4,4,6-pentamethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 781)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.25 (6H, brs), 1.39 (6H, brs), 2.32 (3H, s), 6.26 (1H, d, J = 8.2 Hz), 6.82 ( 1H, dd, J = 8.2Hz, 1.8Hz), 7.17 (1H, d, J = 1.8Hz), 7.57 (1H, dd, J = 7.9Hz, 6.9Hz), 7.75 (1H, dd, J = 8.4Hz , 6.9Hz), 7.81 (1H, d, J = 7.9Hz), 8.07 (1H, d, J = 2.1Hz), 8.17 (1H, d, J = 8.4Hz), 8.70 (1H, d, J = 2.1 Hz).

Example 59
4,4,8-Trimethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 883)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.41 (6H, s), 1.61 (3H, s), 2.65 (2H, s), 6.99 (1H, d, J = 7.6 Hz), 7.14 ( 1H, t, J = 7.6Hz), 7.28 (1H, d, J = 7.6Hz), 7.54 (1H, dd, J = 8.2Hz, 6.9Hz), 7.71 (1H, dd, J = 8.2Hz, 6.9Hz ), 7.75 (1H, d, J = 8.2Hz), 7.93 (1H, d, J = 2.1Hz), 8.11 (1H, d, J = 8.2Hz), 8.79 (1H, d, J = 2.1Hz).

Example 60
3,4,4,8-tetramethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 884)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.27 (3H, d, J = 7.1 Hz), 1.42 (3H, s), 1.61 (6H, s), 2.64 (1H, q, J = 7.1 Hz), 6.31 (1H, d, J = 8.2Hz), 6.99 (1H, d, J = 7.7Hz), 7.14 (1H, t, J = 7.7Hz), 7.28 (1H, d, J = 7.7Hz) , 7.53 (1H, t, J = 7.1Hz), 7.66-7.75 (2H, m), 8.10 (1H, d, J = 8.4Hz), 8.78 (1H, brs).

Example 61
3,3,4,4,8-pentamethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 887)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.00 (3H, s), 1.27 (3H, s), 1.31 (3H, s), 1.41 (3H, s), 1.59 (3H, s), 6.99 (1H, d, J = 7.6Hz), 7.13 (1H, t, J = 7.6Hz), 7.25 (1H, d, J = 7.6Hz), 7.52 (1H, dd, J = 8.2Hz, 7.2Hz) , 7.66-7.75 (2H, m), 8.10 (1H, d, J = 8.2Hz), 8.38 (1H, brs), 9.12 (1H, brs).

Example 62
8-chloro-4,4,5-trimethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 936)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.52 (6H, s), 2.56 (3H, s), 2.67 (2H, s), 6.93 (1H, d, J = 8.2 Hz), 7.05 ( 1H, d, J = 8.2Hz), 7.51 (1H, dd, J = 8.2Hz, 6.9Hz), 7.65-7.76 (2H, m), 7.76 (1H, brs), 8.09 (1H, d, J = 8.2 Hz), 8.79 (1H, brs).

Example 63
8-chloro-3,4,4,5-tetramethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 937)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.19 (3H, brs), 1.45 (3H, brs), 1.54 (3H, brs), 2.40-2.55 (1H, m), 2.54 (3H, s ), 6.93 (1H, d, J = 8.2Hz), 7.04 (1H, d, J = 8.2Hz), 7.50 (1H, dd, J = 8.2Hz, 7.0Hz), 7.47-7.78 (3H, m), 8.19 (1H, d, J = 8.2Hz), 8.74 (1H, brs).

Example 64
5-Methoxy-3-methyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 956)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.39 (3H, d, J = 7.1 Hz), 2.68-2.89 (2H, m), 3.32 (1H, dd, J = 15.0 Hz, 5.0 Hz) , 3.89 (3H, s), 5.98 (1H, d, J = 8.2Hz), 6.64 (1H, d, J = 8.2Hz), 6.99 (1H, t, J = 8.2Hz), 7.59 (1H, dd, J = 8.2Hz, 7.0Hz), 7.77 (1H, dd, J = 8.2Hz, 7.0Hz), 7.82 (1H, d, J = 8.2Hz), 8.10 (1H, d, J = 2.4Hz), 8.16 ( 1H, d, J = 8.2Hz), 8.71 (1H, d, J = 2.4Hz).

Example 65
5-Methoxy-3,3-dimethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 961)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.33 (6H, s), 2.99 (2H, s), 3.88 (3H, s), 5.94 (1H, d, J = 8.2 Hz), 6.63 ( 1H, d, J = 8.2Hz), 6.98 (1H, t, J = 8.2Hz), 7.58 (1H, dd, J = 7.9Hz, 6.9Hz), 7.76 (1H, dd, J = 8.4Hz, 6.9Hz ), 7.82 (1H, d, J = 7.9Hz), 8.08 (1H, d, J = 2.1Hz), 8.17 (1H, d, J = 8.4Hz), 8.69 (1H, d, J = 2.1Hz).

Example 66
3-ethyl-5-methoxy-3-methyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 962)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 0.98 (3H, t, J = 7.4 Hz), 1.31 (3H, s), 1.54-1.80 (2H, m), 2.87 (1H, d, J = 16.6Hz), 3.12 (1H, d, J = 16.6Hz), 3.88 (3H, s), 5.93 (1H, d, J = 8.2Hz), 6.63 (1H, d, J = 8.2Hz), 6.97 ( 1H, t, J = 8.2Hz), 7.58 (1H, dd, J = 8.2Hz, 6.9Hz), 7.76 (1H, dd, J = 8.4Hz, 6.9Hz), 7.82 (1H, d, J = 8.2Hz ), 8.06 (1H, d, J = 2.4Hz), 8.17 (1H, d, J = 8.4Hz), 8.68 (1H, d, J = 2.4Hz).

Example 67
5-Methoxy-3-methyl-3-propyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 963)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 0.92 (3H, t, J = 7.1 Hz), 1.32 (3H, s), 1.36-1.70 (4H, m), 2.87 (1H, d, J = 16.4Hz), 3.12 (1H, d, J = 16.4Hz), 3.88 (3H, s), 5.93 (1H, d, J = 8.2Hz), 6.63 (1H, d, J = 8.2Hz), 6.98 ( 1H, t, J = 8.2Hz), 7.58 (1H, dd, J = 7.9Hz, 7.1Hz), 7.76 (1H, dd, J = 8.4Hz, 7.1Hz), 7.82 (1H, d, J = 7.9Hz ), 8.06 (1H, d, J = 2.4Hz), 8.17 (1H, d, J = 8.4Hz), 8.68 (1H, d, J = 2.4Hz).

Example 68
Ethyl 5-methoxy-3-methyl-2-oxo-3,4-dihydro-2H-1,3′-biquinoline-3-carboxylate (Compound No. 977)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.11 (3H, t, J = 7.2 Hz), 1.64 (3H, s), 2.86 (1H, d, J = 16.1 Hz), 3.80 (1H, d, J = 16.1Hz), 3.88 (3H, s), 4.06-4.19 (2H, m), 5.95 (1H, d, J = 8.2Hz), 6.62 (1H, d, J = 8.2Hz), 6.99 ( 1H, t, J = 8.2Hz), 7.59 (1H, dd, J = 8.2Hz, 6.9Hz), 7.78 (1H, dd, J = 8.4Hz, 6.9Hz), 7.83 (1H, d, J = 8.2Hz ), 8.13 (1H, d, J = 2.1Hz), 8.18 (1H, d, J = 8.4Hz), 8.75 (1H, d, J = 2.1Hz).

Example 69
6-methoxy-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 1008)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 2.87 (2H, dd, J = 8.5 Hz, 5.8 Hz), 3.10 (2H, dd, J = 8.5 Hz, 5.8 Hz), 3.77 (3H, s ), 6.30 (1H, d, J = 9.0Hz), 6.57 (1H, dd, J = 9.0Hz, 2.9Hz), 6.82 (1H, d, J = 2.9Hz), 7.59 (1H, dd, J = 7.7 Hz, 7.1Hz), 7.77 (1H, dd, J = 8.4Hz, 7.1Hz), 7.83 (1H, d, J = 7.7Hz), 8.13 (1H, d, J = 2.4Hz), 8.16 (1H, d , J = 8.4Hz), 8.74 (1H, d, J = 2.4Hz).

Example 70
3-methyl-2-oxo-3,4-dihydro-2H-1,3′-biquinoline-5-carboxylic acid (Compound No. 1173)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.30 (6H, s), 3.46 (2H, s), 6.53 (1H, d, J = 8.0 Hz), 7.12 (1H, t, J = 8.0 Hz), 7.60 (1H, dd, J = 8.2Hz, 7.4Hz), 7.70 (1H, d, J = 8.0Hz), 7.76-7.85 (2H, m), 8.13 (1H, d, J = 1.6Hz) , 8.22 (1H, d, J = 8.2Hz), 8.72 (1H, d, J = 1.6Hz).

Example 71
Methyl 3-methyl-2-oxo-3,4-dihydro-2H-1,3′-biquinoline-5-carboxylate (Compound No. 1221)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.39 (3H, d, J = 6.9 Hz), 2.75-2.89 (1H, m), 3.14 (1H, dd, J = 16.6 Hz, 12.1 Hz) , 3.74 (1H, dd, J = 16.6Hz, 5.3Hz), 3.96 (3H, s), 6.56 (1H, d, J = 7.9Hz), 7.09 (1H, t, J = 7.9Hz), 7.58-7.63 (2H, m), 7.78 (1H, dd, J = 8.4Hz, 7.1Hz), 7.83 (1H, d, J = 8.2Hz), 8.10 (1H, d, J = 2.4Hz), 8.17 (1H, d , J = 8.4Hz), 8.70 (1H, d, J = 2.4Hz).

Example 72
Methyl 3,3-dimethyl-2-oxo-3,4-dihydro-2H-1,3′-biquinoline-5-carboxylate (Compound No. 1226)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.32 (6H, s), 3.41 (2H, s), 3.96 (3H, s), 6.52 (1H, d, J = 8.0 Hz), 7.09 ( 1H, t, J = 8.0Hz), 7.57-7.63 (2H, m), 7.78 (1H, dd, J = 8.4Hz, 6.9Hz), 7.83 (1H, d, J = 8.4Hz), 8.09 (1H, d, J = 2.4Hz), 8.18 (1H, d, J = 8.4Hz), 8.68 (1H, d, J = 2.4Hz).

Example 73
3,3-Dimethyl-2-oxo-3,4-dihydro-2H-1,3′-biquinoline-5-carboxamide (Compound No. 1279)
¹ H-NMR (270 MHz, DMSO-d6) δ (ppm): 1.18 (6H, s), 3.10 (2H, s), 6.33 (1H, dd, J = 7.2 Hz, 2.4 Hz), 7.40-7.48 (2H , m), 7.83 (1H, brs), 8.72 (1H, dd, J = 8.2Hz, 7.0Hz), 8.15-8.21 (2H, m), 8.37 (1H, d, J = 8.4Hz), 8.43 (1H , d, J = 8.4Hz), 8.68 (1H, d, J = 2.4Hz), 9.00 (1H, d, J = 2.4Hz).

Example 74
3-Methyl-2-oxo-3,4-dihydro-2H-1,3′-biquinoline-5-carbonitrile (Compound No. 1327)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.43 (3H, d, J = 6.6 Hz), 2.88-3.02 (1H, m), 3.11 (1H, dd, J = 16.0 Hz, 11.8 Hz) , 3.46 (1H, dd, J = 16.0Hz, 5.4Hz), 6.61 (1H, dd, J = 8.2Hz, 0.8Hz), 7.14 (1H, t, J = 8.2Hz), 7.36 (1H, dd, J = 8.2Hz, 0.8Hz), 7.62 (1H, dd, J = 7.9Hz, 6.9Hz), 7.77-7.86 (2H, m), 8.10 (1H, d, J = 2.1Hz), 8.18 (1H, d, J = 8.4Hz), 8.69 (1H, d, J = 2.1Hz).

Example 75
3,3-Dimethyl-2-oxo-3,4-dihydro-2H-1,3′-biquinoline-5-carbonitrile (Compound No. 1332)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.37 (6H, s), 3.24 (2H, s), 6.57 (1H, d, J = 8.0 Hz), 7.14 (1H, t, J = 8.0 Hz), 7.36 (1H, d, J = 8.0Hz), 7.62 (1H, dd, J = 8.2Hz, 7.4Hz), 7.81 (1H, dd, J = 8.2Hz, 7.4Hz), 7.84 (1H, d , J = 8.2Hz), 8.08 (1H, d, J = 2.4Hz), 8.19 (1H, d, J = 8.2Hz), 8.67 (1H, d, J = 2.4Hz).

Example 76
5- (hydroxymethyl) -3,3-dimethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one (Compound No. 1385)
¹ H-NMR (270 MHz, CDCl ₃ ) δ (ppm): 1.32 (6H, s), 2.16 (1H, brs), 3.07 (2H, s), 4.78 (2H, s), 6.28 (1H, d, J = 7.6Hz), 7.01 (1H, t, J = 7.6Hz), 7.09 (1H, d, J = 7.6Hz), 7.60 (1H, dd, J = 8.2Hz, 7.4Hz), 7.78 (1H, dd, J = 8.2Hz, 7.4Hz), 7.83 (1H, d, J = 8.2Hz), 8.09 (1H, d, J = 2.1Hz), 8.17 (1H, d, J = 8.2Hz), 8.59 (1H, d , J = 2.1Hz).

Formulation Example 1
Powder: 1.0 part by mass of the compound of Example 3, alkyl ether phosphate ester (Dorres A Nippon Kayaku Co., Ltd.) 0.4 part by mass, white carbon (Carplex # 80-D, manufactured by Shionogi Pharmaceutical Co., Ltd.) After mixing 1.5 parts by mass, 0.5 parts by mass of calcium carbonate (manufactured by Adachi Lime Co., Ltd.) and 32.1 parts by mass of meteorite powder (Keiwa clay-style steel, Keiwa Furnace Co., Ltd.), a hammer mill ( Ek sample KII-1 type, manufactured by Fuji Powder Co., Ltd.) and 1.5 times the amount of DL clay (Clay Keiwa, Keiwa Furnace Co., Ltd.) with respect to the mass of the obtained pulverized product In addition, mixing was performed to obtain a powder DL in which scattering was prevented.

Formulation Example 2
Emulsion 10 parts by mass of the compound of Example 3 were dissolved in a mixed solution of 40 parts by mass of xylene (manufactured by Wako Pure Chemical Industries, Ltd.) and 35 parts by mass of DMSO (manufactured by Wako Pure Chemical Industries, Ltd.), and this solution was mixed with an anionic surfactant. 25 parts by mass of a nonionic surfactant mixture (mixing ratio, about 1: 2) (Parakol KPS, manufactured by Nippon Emulsifier Co., Ltd.) was added and mixed to obtain an emulsion.

Formulation Example 3
Wettable powder 1 part by weight of the compound of Example 3, 10 parts by weight of white carbon, 2 parts by weight of polyvinyl alcohol (GOHSENOL GL05, manufactured by Nippon Synthetic Chemical Co., Ltd.), dioctylsulfosuccinic acid sodium salt (Newcol 291PG, manufactured by Nippon Emulsifier Co., Ltd.) ) 0.5 part by mass, 5 parts by mass of linear alkylbenzene sulfonic acid sodium salt (Neogen powder, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 10 parts by mass of calcined diatomaceous earth (Radiolite # 200, manufactured by Showa Chemical Industry Co., Ltd.) 71.5 parts by mass of kaolinite clay (H derivative, manufactured by Keiwa Furnace Co., Ltd.) was sufficiently mixed and pulverized with a hammer mill to obtain a wettable powder.

Formulation Example 4
Granules 2 parts by mass of the compound of Example 3, 2 parts by mass of sodium tripolyphosphate (manufactured by Mitsui Chemicals), 1.5 parts by mass of dextrin (Amicol NO.1, manufactured by Nippon Starch Chemical Co., Ltd.), bentonite (Toyoshun Mining) Co., Ltd.) 25 parts by mass and calcium carbonate (Calhin 600, manufactured by Adachi Lime Co., Ltd.) 69.5 parts by mass, and using a granulator (Dome Gran, Fuji Paudal Co., Ltd., screen 0.9 mmφ). Extruded and granulated. The obtained granulated material was dried with a shelf dryer (manufactured by Tabai Co., Ltd., PERFECT OVEN PS-222 type, 60 ° C.) and then sieved to 600 to 1180 μm to obtain granules.

Test example 1
Rice blast control trial (therapeutic effect)
The third to fourth leaf stage plant cultivation test plant (rice: Kofu) is spray-inoculated with a spore suspension of pathogenic bacteria (Magnaporte glycia), and the pot is placed in an inoculation room with a room temperature of 20-23 ° C. Urged. One day after inoculation, the compound of the present invention was dissolved in a dimethyl sulfoxide-methanol mixed solution (volume ratio: 9/1), and a spray solution containing 300 ppm of the compound of the present invention was prepared and sprayed uniformly in the pot. The severity of the disease 7 days after the inoculation was investigated. The test was performed in duplicate.
In addition, the disease severity was determined by the following criteria by visually observing the disease severity of the test plant, and expressed in 4 stages of 0 to 3.
The degree of disease is 0: There is no disease.
1: The degree of disease is less than 40% of the untreated area.
2: The onset degree is 40% or more and less than 80%.
3: The onset degree is 80% or more.
As a result of this test, Example 2 (Compound No. 7), Example 3 (Compound No. 622), Example 4 (Compound No. 2), Example 5 (Compound No. 8), Example 6 (Compound No. 9), Example 7 (Compound No. 11), Example 8 (Compound No. 39), Example 11 (Compound No. 60), Example 12 (Compound No. 61), Example 13 (Compound No. 62), Example 14 (Compound) No. 64), Example 15 (Compound No. 69), Example 17 (Compound No. 76), Example 19 (Compound No. 88), Example 20 (Compound No. 89), Example 21 (Compound No. 92), Example 26 (Compound No. 117), Example 29 (Compound No. 142), Example 30 (Compound No. 145), Example 41 (Compound No. 248), Example 42 (Compound No. 251), Example 48 (Compound No.) 288), Example 49 (Compound No. 410), Example 52 (Compound No. 619), Example 54 (Compound No. 724), Example 55 (Compound No. 725), Example 58 (Compound No. 781), Example 64 (Compound) No. 956), Example 65 (Compound No. 961), and Example 72 (Compound No. 1226) had a disease severity of 0.

Test example 2
Tomato gray mold control test (preventive effect)
Disperse liquid containing 300 ppm of the compound of the present invention by dissolving the compound of the present invention in dimethyl sulfoxide and methanol (volume ratio 9: 1) in a pot cultivation test plant in the second to third leaf stages (tomato: large-scale longevity) Sprayed on. After cultivating for one day, the pot (Botrytis cinerea) was spray-inoculated with the pathogen spore suspension, and the pot was placed in an inoculation room having a room temperature of 20 to 23 degrees to promote disease. The degree of disease onset 2 days after the inoculation was investigated. The test was performed in duplicate.
In addition, the disease severity was determined by the following criteria by visually observing the disease severity of the test plant, and expressed in 4 stages of 0 to 3.
The degree of disease is 0: There is no disease.
1: The degree of disease is less than 40% of the untreated area.
2: The onset degree is 40% or more and less than 80%.
3: The onset degree is 80% or more.
As a result of this test, Example 3 (Compound No. 622), Example 20 (Compound No. 89), Example 21 (Compound No. 92), Example 23 (Compound No. 113), Example 25 (Compound No. 115), Example 26 (Compound No. 117), Example 27 (Compound No. 129), Example 29 (Compound No. 142), Example 30 (Compound No. 145), Example 31 (Compound No. 161), Example 41 (Compound) No. 248), Example 42 (Compound No. 251), Example 52 (Compound No. 619), Example 57 (Compound No. 778), Example 58 (Compound No. 781), Compound of Example 64 (Compound No. 956) The disease severity was 0.

The compound of the present invention can be used as an agricultural and horticultural fungicide, and is effective against various phytopathogenic fungi, particularly rice blast, without causing damage to the host plant. It is excellent.
Examples of plant diseases for which the compound of the present invention exhibits excellent efficacy include rice blast (Magnapolla glycia) and gray mold of cucumber, tomato and kidney beans (Botrytis cinerea). Is not limited to these.

Claims (10)

General formula

Where
Ra, Rb, Rc and Rd may be the same or different,
Hydrogen atom; halogen atom; hydroxyl group; C ₁ -C ₆ alkoxy group; acyl group; carboxyl group; cyano group; acyloxy group; halogen atom, hydroxyl group, C ₁ -C ₆ alkoxy group, C ₁ -C ₆ alkylthio group, C ₁ -C ₆ alkylsulfinyl group, C ₁ -C ₆ alkylsulfonyl group and the same or different 1-3 and which may be C ₁ -C ₆ alkyl group substituted with a substituent selected from the group consisting of a phenoxy group; a halogen atom, the same selected hydroxyl, C ₁ -C ₆ alkoxy group, C ₁ -C ₆ alkylthio group, C ₁ -C ₆ alkylsulfinyl groups, C ₁ -C ₆ alkylsulfonyl group, from the group consisting of phenyl and phenoxy groups or different 1-3 may be substituted with a substituent C ₂ -C ₆ alkenyl group; a halogen atom, a hydroxyl group, C ₁ -C ₆ alkoxy group, C ₁ -C ₆ Alkylthio group, C ₁ -C ₆ alkylsulfinyl group, C ₁ -C ₆ alkylsulfonyl group, or C ₂ to be substituted by the same or different 1 to 3 substituents selected from the group consisting of phenyl and phenoxy groups -C ₆ alkynyl group; a halogen atom, the same or different 1 to 3 may C ₁ -C ₆ alkyl group substituted by a halogen atom, C ₁ -C ₆ alkoxy group, a nitro group, a cyano group, a hydroxyl group, and the same Or an aryl group which may be substituted with the same or different 1 to 5 substituents selected from the group consisting of different 1 to 2 C ₁ -C ₆ alkyl groups or an amino group which may be substituted with an acyl group; halogen atoms, the same or different 1-3 is substituted with a halogen atom or C ₁ -C ₆ alkyl group, C ₁ -C ₆ alkoxy group, a nitro group, a cyano group, a hydroxyl group及Same or different one to two C ₁ -C ₆ alkyl group or the same or different 1 to 6 substituted with a substituent which may be aralkyl group selected from the group consisting of amino group which may be substituted with an acyl group Or
A group consisting of a halogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group, and a phenoxy group, which are formed together with carbon atoms or alkylenes to which R a and R b, R c and R d or R b and R c are bonded. represent the same or different and may be substituted with 1-3 substituents C ₃ -C ₁₀ cycloalkyl ring selected from,
X may be the same or different;
A halogen atom; a hydroxyl group; C ₁ -C ₆ alkoxy group; an acyl group; a carboxyl group; a cyano group; an acyloxy group; nitro group; C ₁ -C ₆ alkylthio group; C ₁ -C ₆ alkylsulfinyl group; C ₁ -C ₆ an alkylsulfonyl group; a halogen atom, a hydroxyl group, C ₁ -C ₆ alkoxy group, selected from C ₁ -C ₆ alkylthio group, C ₁ -C ₆ alkylsulfinyl group, the group consisting of C ₁ -C ₆ alkylsulfonyl group and a phenoxy group C ₁ -C ₆ alkyl group which may be substituted with the same or different 1 to 3 substituents; halogen atom, hydroxyl group, C ₁ -C ₆ alkoxy group, C ₁ -C ₆ alkylthio group, C ₁ -C ₆ alkylsulfinyl group, still at C ₁ -C ₆ alkylsulfonyl group, the same or different 1 to 3 substituents selected from the group consisting of phenyl and phenoxy groups And which may be C ₂ -C ₆ alkenyl group; a halogen atom, a hydroxyl group, C ₁ -C ₆ alkoxy group, C ₁ -C ₆ alkylthio group, C ₁ -C ₆ alkylsulfinyl group, C ₁ -C ₆ alkylsulfonyl group, same or different 1-3 is substituted with a substituent which may C ₂ to -C ₆ alkynyl group selected from the group consisting of phenyl group and a phenoxy group; a halogen atom, the same or different 1 to 3 halogen atoms which may be substituted C ₁ -C ₆ alkyl group, C ₁ -C ₆ alkoxy group, a nitro group, a cyano group, a hydroxyl group and the same or different one to two C ₁ -C ₆ alkyl group or an acyl group An aryl group which may be substituted with the same or different 1 to 5 substituents selected from the group consisting of optionally amino groups; a halogen atom, the same or different 1 to 3 halogen atoms In which may be substituted C ₁ -C ₆ alkyl and C ₁ -C ₆ same or different 1-6 is substituted with a substituent which may heteroaryl group selected from the group consisting of an alkoxy group; the same or different represents one to two C ₁ -C ₆ alkyl group or amino group which may be substituted with an acyl group,
Y are identical or may be different, represents a halogen atom, C ₁ -C ₆ alkyl group, a substituent selected from the group consisting of C ₁ -C ₆ alkoxy group and a hydroxyl group,
m represents an integer of 0 to 4,
n represents an integer of 0 to 6,
Or a salt thereof. Ra, Rb, Rc and Rd may be the same or different, and are composed of a hydrogen atom; a halogen atom; a C _{2 to} C ₇ alkoxycarbonyl group; a halogen atom, a hydroxyl group, a C _{1 to} C ₆ alkoxy group and a phenoxy group. may be substituted with same or different 1 to 3 substituents selected from the group C ₁ -C ₆ alkyl group; or a halogen atom, or C ₁ which are substituted with same or different 1 to 3 halogen atoms -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group, a nitro group, the same or different 1-5 is substituted with a substituent which may be aryl group selected from the group consisting of cyano group and a hydroxyl group, claims 2. The compound or salt thereof according to 1. Ra, Rb, Rc and Rd may be the same or different, and are a hydrogen atom; a C ₂ -C ₃ alkoxycarbonyl group; or a C _1- which may be substituted with the same or different 1 to 3 halogen atoms. is a C ₄ alkyl group, compound or salt thereof according to claim 1.   Ra, Rb, Rc and Rd may be the same or different and are each a hydrogen atom; a methyl group; an ethyl group; a propyl group; a butyl group; or an ethoxycarbonyl group. Or a salt thereof. X _m may be the same or different and X is a halogen atom; a C ₁ -C ₆ alkyl group which may be substituted with 1 to 3 halogen atoms which are the same or different; C ₁ -C ₆ alkoxy group ; or a _C 2 -C ₃ alkoxycarbonyl group, m is 0-2, or a salt thereof according to any one of claims 1 to 4. The compound according to any one of claims 1 to 5, wherein X _m is X is a fluorine atom, a chlorine atom, a methyl group, a methoxy group or a methoxycarbonyl group, and m is 0, 1 or 2. Or a salt thereof. Y _n is, Y is a fluorine atom, a chlorine atom or a methyl radical, n is 0 or 1, compound or salt thereof according to any one of claims 1 to 6. The compound or a salt thereof according to any one of claims 1 to 6, wherein Y _n is a methyl group, and n is 0 or 1. 5-fluoro-3,4,4-trimethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one,
5-fluoro-3,3,4,4-tetramethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one,
3-butyl-6-fluoro-3-methyl-3,4-dihydro-2H-1,3′-biquinolin-2-one,
6-fluoro-3,4,4-trimethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one,
6-fluoro-3,3,4,4-tetramethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one,
8-fluoro-3,4,4-trimethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one,
8-fluoro-3,3,4,4-tetramethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one,
5,8-difluoro-3,4,4-trimethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one,
5,8-difluoro-3,3,4,4-tetramethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one,
3,3,4,4,6-pentamethyl-3,4-dihydro-2H-1,3′-biquinolin-2-one,
The compound or salt thereof according to claim 1, which is 5-methoxy-3-methyl-3,4-dihydro-2H-1,3'-biquinolin-2-one or a salt thereof.   An agrochemical containing the compound according to any one of claims 1 to 9 or a salt thereof as an active ingredient.