JP2010502661A - Fungicide - Google Patents

Abstract

  The compounds of the general formula whose substituents are defined in claim (1) are useful as fungicides.

Description

  The present invention relates to novel quinolinyloxyalkanoic acid amides, methods for their preparation, compositions containing them, and methods for eradicating fungal infections using them, particularly plant fungal infections.

  Certain quinolinyloxyalkanoic acid amide derivatives and their use as agricultural and horticultural fungicides are disclosed, for example, in WO 04/047538 and JP 2001-89453.

  The present invention relates to the provision of certain substituted quinolin-6-yloxyalkanoic acid amides for primary use as plant fungicides.

（式中、Ｑ¹、Ｑ²及びＱ³は、互いに独立して、ハロゲン、シアノ、ニトロ、アジド、任意に置換されたＣ_1-6アルキル、任意に置換されたＣ_3-6シクロアルキル、硫黄、酸素もしくはＮＲ⁰（式中、Ｒ⁰は、水素又は任意に置換されたＣ_1-6アルキルである。）から選択された少なくとも１個のヘテロ原子を含む任意に置換されたＣ_3-6−複素環式基、任意に置換されたＣ_3-6シクロアルキル（Ｃ_1-4）アルキル、任意に置換されたＣ_2-6アルケニル、任意に置換されたＣ_2-6アルキニル、任意に置換されたＣ_1-6アルコキシ、任意に置換されたＣ_2-6アルケニルオキシ、任意に置換されたＣ_2-6アルキニルオキシ、任意に置換されたアリール、任意に置換されたアリールオキシ、任意に置換されたアリール（Ｃ_1-6）アルキル、任意に置換されたアリール（Ｃ_1-6）アルコキシ、任意に置換されたヘテロアリール、任意に置換されたヘテロアリールオキシ、任意に置換されたヘテロアリール（Ｃ_1-6）アルキル、任意に置換されたヘテロアリール（Ｃ_1-6）アルコキシ、−ＳＦ₅又は−Ｓ（Ｏ）_u（Ｃ_1-6）アルキル（式中、ｕは０、１もしくは２であり、及びアルキル基は、ハロゲンにより任意に置換されている。）であるか、又は
Ｑ¹、Ｑ²及びＱ³は、互いに独立して、−ＯＳＯ₂（Ｃ_1-4）アルキル（式中、アルキル基は、ハロゲンにより任意に置換されている。）であるか、又は
Ｑ¹、Ｑ²及びＱ³は、互いに独立して、−ＣＯＮＲ^UＲ^V、−ＣＯＲ^U、−ＣＯ₂Ｒ^U、−ＣＲ^U＝ＮＲ^V、−ＮＲ^UＲ^V、−ＮＲ^UＣＯＲ^V、−ＮＲ^UＣＯ₂Ｒ^V、−ＳＯ₂ＮＲ^UＲ^V又は−ＮＲ^UＳＯ₂Ｒ^Wである（式中、Ｒ^Wは、任意に置換されたＣ_1-6アルキルであり、並びにＲ^U及びＲ^Vは、互いに独立して、水素又はハロゲンにより任意に置換されたＣ_1-6アルキルであるか、又は−ＣＯＮＲ^UＲ^Vもしくは−ＳＯ₂ＮＲ^UＲ^Vの場合、Ｒ^UＲ^Vは、結合され、５−もしくは６−員の炭素環、もしくは硫黄、酸素及びＮＲ⁰（式中、Ｒ⁰は、水素又は任意に置換されたＣ_1-6アルキルである。）から選択されたヘテロ原子を含む複素環を形成してよいか、又は−ＣＲ^U＝ＮＲ^Vの場合、Ｒ^Vは、ヒドロキシもしくは任意に置換されたＣ_1-6アルコキシ、任意に置換されたアリールオキシ又は任意に置換されたヘテロアリールオキシである。）か、又は
Ｑ¹及びＱ²は、互いに独立して、追加的に水素を意味し、
Ｒ¹は、任意に置換されたＣ_1-4アルキル、任意に置換されたＣ_2-4アルケニル、任意に置換されたＣ_2-4アルキニル、又は任意に置換されたＣ_3-4シクロアルキルであり、
Ｒ²は、水素、Ｃ_1-8アルキル、Ｃ_3-4シクロアルキル、Ｃ_2-8アルケニル、シアノ、ヒドロキシ、アルコキシ、シアノ（Ｃ_1-4）アルキル、Ｃ_1-4アルコキシ（Ｃ_1-4）アルキル、Ｃ_1-4アルコキシ（Ｃ_1-4）アルコキシ（Ｃ_1-4）アルキル、又はベンジルオキシ（Ｃ_1-4）アルキルであり、ここでフェニル環は、Ｃ_1-4アルコキシにより任意に置換されており、
Ｒ³は、−（ＣＲ^aＲ^b）_p（ＣＲ^cＲ^d）_q（Ｘ）_r（ＣＲ^eＲ^f）_sＲ⁴であり、ここで
Ｒ^a、Ｒ^b、Ｒ^c、Ｒ^d、Ｒ^e及びＲ^fは、互いに独立して、水素、Ｃ_1-4アルキル、ハロゲン、シアノ、ヒドロキシ、Ｃ_1-4アルコキシ、もしくはＣ_1-4アルコキシカルボニルであるか、又は
Ｒ^aＲ^b、Ｒ^cＲ^d又はＲ^eＲ^fは、結合して、３〜８員の炭素環、もしくは硫黄、酸素及びＮＲ⁰（式中、Ｒ⁰は、水素又は任意に置換されたＣ_1-6アルキルである。）から選択されたヘテロ原子を含む複素環を形成してよく、
Ｘは、（ＣＯ）、（ＣＯ）Ｏ、Ｏ（ＣＯ）、Ｏ、Ｓ（Ｏ）_tであり、ここでｔは、０、１もしくは２であるか、又はＸは、ＮＨもしくはＮ（Ｃ_1-6）アルキルであり、
ｐ、ｒ及びｓは、互いに独立して、０もしくは１であり、
ｑは、０、１もしくは２であり、
Ｒ⁴は、任意に置換されたＣ_1-6アルキル、任意に置換されたＣ_2-6アルケニル、−ＣＲ^UU＝ＮＲ^VV（式中、Ｒ^uuは、水素もしくはＣ_1-6アルキルであり、及びＲ^VVは、ヒドロキシ又は任意に置換されたＣ_1-6アルコキシ、任意に置換されたアリールオキシもしくは任意に置換されたヘテロアリールオキシである。）、又は−ＣＨ₂−Ｃ≡Ｃ−Ｒ⁵であり、ここで、
Ｒ⁵は、水素、ハロゲン、ヒドロキシ、Ｃ_1-6アルコキシ、Ｃ_1-3アルコキシ（Ｃ_1-3）アルコキシ、シアノ、Ｃ_1-4アルキルカルボニルオキシ、アミノカルボニルオキシ、モノ−もしくはジ（Ｃ_1-4）−アルキルアミノカルボニルオキシ、トリ（Ｃ_1-4）アルキルシリルオキシ、又は−Ｓ（Ｏ）_g（Ｃ_1-6）アルキル（式中、ｇは、０、１もしくは２である。）により任意に置換されたＣ_1-8アルキルであるか、又は
Ｒ⁵は、ハロゲン、ヒドロキシ、Ｃ_1-6アルコキシ、Ｃ_1-3アルコキシ−（Ｃ_1-3）アルコキシ、シアノ、Ｃ_1-4アルキルカルボニルオキシ、アミノカルボニルオキシ、モノ−もしくはジ（Ｃ_1-4）アルキル−アミノカルボニルオキシ、トリ（Ｃ_1-4）アルキルシリルオキシ、又は−Ｓ（Ｏ）_g（Ｃ_1-6）アルキル（式中、ｇは、０、１もしくは２である。）により任意に置換されたＣ_3-6シクロアルキルであるか、又は
Ｒ⁵は、Ｃ_3-6シクロアルキル（Ｃ_1-4）アルキルであり、ここでアルキル及び／又はシクロアルキル部分は、ハロゲン、ヒドロキシ、Ｃ_1-6アルコキシ、Ｃ_1-3アルコキシ（Ｃ_1-3）アルコキシ、シアノ、Ｃ_1-4アルキルカルボニルオキシ、アミノカルボニルオキシ、モノ−もしくはジ（Ｃ_1-4）アルキルアミノカルボニルオキシ、トリ（Ｃ_1-4）アルキル−シリルオキシ、もしくは−Ｓ（Ｏ）_g（Ｃ_1-6）アルキル（式中、ｇは、０、１もしくは２である。）により任意に置換されているか、又は
Ｒ⁵は、任意に置換されたアリール、任意に置換されたアリール（Ｃ_1-4）アルキル、任意に置換されたアリールオキシ（Ｃ_1-4）アルキル、任意に置換されたヘテロアリール、もしくは任意に置換されたヘテロアリール（Ｃ_1-4）アルキル、もしくは任意に置換されたヘテロアリールオキシ（Ｃ_1-4）アルキルであるか、又は
Ｒ⁴は、任意に置換されたＣ_3-6シクロアルキル、任意に置換されたＣ_5-6シクロアルケニル、任意に置換されたアリール、任意に置換されたヘテロアリール、もしくは硫黄、酸素もしくはＮＲ⁰（式中、Ｒ⁰は、水素もしくは任意に置換されたＣ_1-6アルキルである。）から選択されたヘテロ原子を任意に含む任意に置換された５−〜８−員環であるか、又は
Ｒ³が、−（ＣＲ^aＲ^b）_p（ＣＲ^cＲ^d）_q（Ｘ）_r（ＣＲ^eＲ^f）_sＲ⁴である場合、Ｒ²及びＲ³は、結合して、ハロゲン、Ｃ_1-4アルキル、モノ−もしくはジ−（Ｃ_1-4）アルキルアミノカルボニルにより任意に置換され、並びに硫黄、酸素及びＮＲ⁰⁰（式中、Ｒ⁰⁰は、ハロゲン、Ｃ_1-6アルコキシもしくはシアノにより任意に置換されたＣ_1-4アルキルであるか、又はＲ⁰⁰は、ニトロ、Ｃ_1-4アルキル、ハロ（Ｃ_1-4）−アルキル、Ｃ_1-4アルキルカルボニルもしくはヘテロアリールにより任意に置換されたフェニルである。）から選択されたヘテロ原子を任意に含む、５−もしくは６−員環を形成するか、又は、Ｒ²及びＲ³は結合し、任意に置換された６，６−員の二環を形成してよく、
Ｒ³は、−（ＣＲ³⁰Ｒ⁴⁰）Ｃ≡ＣＲ⁵⁰であり、ここで
Ｒ³⁰及びＲ⁴⁰は、互いに独立して、水素、Ｃ_1-6アルキル、ハロ（Ｃ_1-4）アルキル、Ｃ_1-4アルコキシ（Ｃ_1-3）アルキル、Ｃ_2-3アルケニル、もしくはＣ_2-3アルキニルであるか、又は
Ｒ³⁰及びＲ⁴⁰は、それらが結合している炭素原子と結合し、３〜６員の炭素環、又は硫黄、酸素もしくはＮＲ⁰⁰⁰（式中、Ｒ⁰⁰⁰は、水素もしくはＣ_1-4アルキルである。）から選択されたヘテロ原子を含む複素環を形成し、ここで炭素環又は複素環は、ハロもしくはＣ_1-4アルキルにより任意に置換されており、
Ｒ⁵⁰は、水素、任意に置換されたＣ_1-4アルキル、任意に置換されたＣ_3-6シクロアルキル、任意に置換されたアリール、もしくは硫黄、酸素もしくはＮＲ⁰⁰⁰（式中、Ｒ⁰⁰⁰は、水素もしくはＣ_1-6アルキルである。）から選択されたヘテロ原子を含む任意に置換されたヘテロアリールであり、
Ｌは、硫黄又は酸素であり、並びに
ｎは、０、１又は２である。）、並びに
式Ｉの化合物の塩及びＮ−酸化物が提供される。 Thus, according to the invention, the compound of general formula I:

Wherein Q ¹ , Q ² and Q ³ are independently of one another halogen, cyano, nitro, azide, optionally substituted C _1-6 alkyl, optionally substituted C _3-6 cycloalkyl, Optionally substituted C ₃ -containing at least one heteroatom selected from sulfur, oxygen or NR ⁰ , wherein R ⁰ is hydrogen or optionally substituted C _1-6 alkyl. ₆ -heterocyclic group, optionally substituted C _3-6 cycloalkyl (C _1-4 ) alkyl, optionally substituted C _2-6 alkenyl, optionally substituted C _2-6 alkynyl, optionally Substituted C _1-6 alkoxy, optionally substituted C _2-6 alkenyloxy, optionally substituted C _2-6 alkynyloxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted aryl (C _1-6) alkyl, optionally substituted aryl (C _1-6) alkoxy, optionally substituted heteroaryl, optionally substituted heteroaryloxy, heteroaryl (C _1-6), optionally substituted alkyl, optionally substituted heteroaryl (C _{1 -6)} alkoxy, -SF _5, or -S (O) _u (C _1-6) alkyl (wherein, u is 0, 1 or 2, and alkyl groups are optionally substituted by halogen. Or Q ¹ , Q ² and Q ³ are, independently of one another, —OSO ₂ (C _1-4 ) alkyl, wherein the alkyl group is optionally substituted with halogen. Or Q ¹ , Q ^2, and Q ³ are independently of each other, —CONR ^U R ^V , —COR ^U , —CO ₂ R ^U , —CR ^U = NR ^V , —NR ^U R ^V , —NR ^U COR ^V , -NR ^U CO ₂ R ^V , -SO ₂ NR ^U R ^V or -NR ^U SO ₂ R ^W where R ^W is optionally substituted C _1-6 alkyl, and R ^U and R ^V , independently of one another, are C _1-6 optionally substituted with hydrogen or halogen. In the case of alkyl or —CONR ^U R ^V or —SO ₂ NR ^U R ^V , R ^U R ^V is bonded to a 5- or 6-membered carbocycle, or sulfur, oxygen and NR ⁰ (formula In which R ⁰ is hydrogen or optionally substituted C _1-6 alkyl.) Or may form a heterocycle containing a heteroatom selected from: or when —CR ^U ═NR ^{V V} is hydroxy or optionally substituted C _1-6 alkoxy, optionally substituted aryloxy or optionally substituted heteroaryloxy. Or Q ¹ and Q ² independently of one another additionally denote hydrogen,
R ¹ is optionally substituted C _1-4 alkyl, optionally substituted C _2-4 alkenyl, optionally substituted C _2-4 alkynyl, or optionally substituted C _3-4 cycloalkyl. Yes,
R ² is hydrogen, C _1-8 alkyl, C _3-4 cycloalkyl, C _2-8 alkenyl, cyano, hydroxy, alkoxy, cyano (C _1-4 ) alkyl, C _1-4 alkoxy (C _1-4 ) Alkyl, C _1-4 alkoxy (C _1-4 ) alkoxy (C _1-4 ) alkyl, or benzyloxy (C _1-4 ) alkyl, wherein the phenyl ring is optionally substituted by C _1-4 alkoxy Has been replaced,
R ³ is — (CR ^a R ^b ) _p (CR ^c R ^d ) _q (X) _r (CR ^e R ^f ) _s R ⁴ , where R ^a , R ^b , R ^c , R ^d , R ^e and R ^f , independently of one another, are hydrogen, C _1-4 alkyl, halogen, cyano, hydroxy, C _1-4 alkoxy, or C _1-4 alkoxycarbonyl, or R ^a R ^b , R ^c R ^d or R ^e R ^f may be combined to form a 3-8 membered carbocyclic ring, or sulfur, oxygen and NR ⁰ , where R ⁰ is hydrogen or optionally substituted C _1-6 alkyl. A heterocyclic ring containing a heteroatom selected from
X is (CO), (CO) O, O (CO), O, S (O) _t , where t is 0, 1 or 2, or X is NH or N (C _1-6 ) is alkyl,
p, r and s are independently of each other 0 or 1,
q is 0, 1 or 2;
R ⁴ is optionally substituted C _1-6 alkyl, optionally substituted C _2-6 alkenyl, —CR ^UU ═NR ^VV , where R ^uu is hydrogen or C _1-6 alkyl; And R ^VV is hydroxy or optionally substituted C _1-6 alkoxy, optionally substituted aryloxy or optionally substituted heteroaryloxy), or —CH ₂ —C≡C—R ^5. And where
R ⁵ is hydrogen, halogen, hydroxy, C _1-6 alkoxy, C _1-3 alkoxy (C _1-3 ) alkoxy, cyano, C _1-4 alkylcarbonyloxy, aminocarbonyloxy, mono- or di (C _{1 -4} ) -alkylaminocarbonyloxy, tri (C _1-4 ) alkylsilyloxy, or —S (O) _g (C _1-6 ) alkyl (wherein g is 0, 1 or 2) Or optionally substituted by C _1-8 alkyl, or R ⁵ is halogen, hydroxy, C _1-6 alkoxy, C _1-3 alkoxy- (C _1-3 ) alkoxy, cyano, C _1-4 Alkylcarbonyloxy, aminocarbonyloxy, mono- or di (C _1-4 ) alkyl-aminocarbonyloxy, tri (C _1-4 ) alkylsilyloxy, or —S (O) _g (C _1-6 ) alkyl ( Where g is 0, 1 if It is 2.) By either a C _3-6 cycloalkyl optionally substituted, or R ⁵ is C _3-6 cycloalkyl (C _1-4) alkyl, wherein alkyl and / or cycloalkyl The alkyl moiety may be halogen, hydroxy, C _1-6 alkoxy, C _1-3 alkoxy (C _1-3 ) alkoxy, cyano, C _1-4 alkylcarbonyloxy, aminocarbonyloxy, mono- or di (C _1-4 ) Alkylaminocarbonyloxy, tri (C _1-4 ) alkyl-silyloxy, or —S (O) _g (C _1-6 ) alkyl, where g is 0, 1 or 2. Substituted or R ⁵ is optionally substituted aryl, optionally substituted aryl (C _1-4 ) alkyl, optionally substituted aryloxy (C _1-4 ) alkyl, optionally substituted Heteroaryl Or optionally substituted heteroaryl (C _1-4 ) alkyl, or optionally substituted heteroaryloxy (C _1-4 ) alkyl, or R ⁴ is optionally substituted C _{3- 6} cycloalkyl, optionally substituted C _5-6 cycloalkenyl, optionally substituted aryl, optionally substituted heteroaryl, or sulfur, oxygen or NR ⁰ , where R ⁰ is hydrogen or optionally . a substituted C _1-6 alkyl) or a 5-～8- membered rings that are optionally substituted, optionally containing a heteroatom chosen from, or R ^3, - (CR ^a R ^b) _{When p} (CR ^c R ^d ) _q (X) _r (CR ^e R ^f ) _s R ⁴ , R ² and R ³ are combined to form a halogen, C _1-4 alkyl, mono- or di- ( C _1-4 ) optionally substituted by alkylaminocarbonyl, and sulfur , Oxygen and NR ^{00 where} R ⁰⁰ is C _1-4 alkyl optionally substituted with halogen, C _1-6 alkoxy or cyano, or R ⁰⁰ is nitro, C _1-4 alkyl, Phenyl optionally substituted with halo (C _1-4 ) -alkyl, C _1-4 alkylcarbonyl or heteroaryl. A 5- or 6-membered ring optionally containing a heteroatom selected from: or R ² and R ³ are joined to form an optionally substituted 6,6-membered bicycle You can,
R ³ is — (CR ³⁰ R ⁴⁰ ) C≡CR ⁵⁰ , wherein R ³⁰ and R ⁴⁰ are independently of each other hydrogen, C _1-6 alkyl, halo (C _1-4 ) alkyl, C _1-4 alkoxy (C _1-3 ) alkyl, C _2-3 alkenyl, or C _2-3 alkynyl, or R ³⁰ and R ⁴⁰ are attached to the carbon atom to which they are attached; Forming a six-membered carbocycle or a heterocycle containing a heteroatom selected from sulfur, oxygen or NR ⁰⁰⁰ , wherein R ⁰⁰⁰ is hydrogen or C _1-4 alkyl, wherein the carbocycle Or the heterocycle is optionally substituted with halo or C _1-4 alkyl;
R ⁵⁰ is hydrogen, optionally substituted C _1-4 alkyl, optionally substituted C _3-6 cycloalkyl, optionally substituted aryl, or sulfur, oxygen or NR ⁰⁰⁰ (where R ⁰⁰⁰ is Optionally substituted heteroaryl containing a heteroatom selected from: hydrogen or C _1-6 alkyl;
L is sulfur or oxygen, and n is 0, 1 or 2. And salts and N-oxides of compounds of formula I are provided.

  The compounds of the present invention contain at least one asymmetric carbon atom and may exist as enantiomers (or as diastereomeric pairs) or mixtures thereof. Further, when n is 1, the compound of the present invention is a sulfoxide, which can exist in two enantiomeric forms, and the adjacent carbon can also exist in two enantiomeric forms. Thus, the compounds of general formula (I) can exist as racemates, diastereomers, or single enantiomers, and the present invention includes all possible isomers or mixtures of isomers in all proportions. For any given compound, it is anticipated that one isomer may be more fungicidal than the other.

N-oxide of the compound of formula I preferably means an N-oxide formed by a quinoline moiety.
The salts that the compounds of formula I can form are preferably those formed by the interaction of these compounds with acids. The term “acid” comprises inorganic acids such as hydrogen halides, sulfuric acid, phosphoric acid, as well as organic acids, preferably the commonly used alkanoic acids such as formic acid, acetic acid and propionic acid.

Except as otherwise noted, alkyl groups and alkyl moieties such as alkoxy, alkylthio, etc., are preferably 1-6, typically 1-4 carbon atoms, in straight or branched chain form. including. Examples are methyl, ethyl, n- and iso-propyl, and n-, sec-, iso- and tert-butyl. When the alkyl moiety contains 5 or 6 carbon atoms, examples include n-pentyl and n-hexyl. Examples of suitable optional substituents for alkyl groups and moieties are halo, hydroxy, C _1-4 alkoxy and C _1-4 alkoxy (C _1-4 ) alkoxy, cyano, optionally substituted aryl and optionally substituted Heteroaryl. When the optional substituent is halo, the haloalkyl group or moiety is typically monochloromethyl, monofluoromethyl, dichloromethyl, difluoromethyl, trichloromethyl or trifluoromethyl.

Except as otherwise noted, alkenyl and alkynyl moieties also preferably contain 2 to 6, typically 2 to 4 carbon atoms in straight or branched chain form. Examples are allyl, ethynyl and propargyl. Optional substituents include halo, alkoxy, optionally substituted aryl and optionally substituted heteroaryl.
Halo includes fluoro, chloro, bromo and iodo.

Aryl is usually phenyl but includes naphthyl, anthryl and phenanthryl.
Heteroaryl is typically a 5- or 6-membered aromatic ring containing one or more sulfur, oxygen or NR moieties as heteroatoms, which is one or more other such as a benzene ring. May be condensed to an aromatic ring or a heteroaromatic ring. Examples are thienyl, furyl, pyrrolyl, isoxazolyl, oxazolyl, thiazolyl, oxadiazolyl, pyrazolyl, imidazolyl, triazolyl, isothiazolyl, tetrazolyl, thiadiazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, benzofuranyl, benzothienyl, dibenzofuranyl, dibenzothienyl , Benzothiazolyl, benzoxazolyl, benzimidazolyl, indolyl, quinolyl, isoquinolyl, quinazolinyl and quinoxalinyl groups and their N-oxides and salts if preferred here. Any aryl or heteroaryl value is optionally substituted. Except where otherwise noted, substituents that may be present include one or more of the following: halo, hydroxy, mercapto, C _1-6 alkyl (especially methyl and ethyl), C _2-6 alkenyl (especially Allyl), C _2-6 alkynyl (particularly propargyl), C _1-6 alkoxy (particularly methoxy), C _2-6 alkenyloxy (particularly allyloxy), C _2-6 alkynyloxy (particularly propargyloxy), halo (C _{1 -6} ) alkyl (especially trifluoromethyl), halo (C _1-6 ) alkoxy (especially trifluoromethoxy), —S (O) _m (C _1-6 ) alkyl (where m is 0, 1 or 2) And alkyl is optionally substituted with halo.), Hydroxy (C _1-6 ) alkyl, C _1-4 alkoxy (C _1-4 ) alkyl, C _1-4 alkoxy (C _1-4). ) alkoxy, C _3-6 cycloalkyl , C _3-6 cycloalkyl (C _1-4) alkyl, optionally substituted aryl (especially optionally substituted phenyl), optionally substituted heteroaryl (especially optionally substituted pyridyl or pyrimidinyl), Optionally substituted aryloxy (especially optionally substituted phenoxy), optionally substituted heteroaryloxy (especially optionally substituted pyridyloxy or pyrimidinyloxy), optionally substituted —S (O) _m Aryl (where m is 0, 1 or 2) (especially optionally substituted phenylthio), optionally substituted —S (O) _m heteroaryl (where m is 0, 1 or 2) ) (especially optionally substituted pyridylthio or pyrimidinylthio), optionally substituted aryl (C _1-4) alkyl (especially optionally substituted benzyl, optionally substituted Phenyl n- propyl (alkyl moiety wherein the optionally substituted by hydroxy.) Substituted phenethyl and optionally), heteroaryl (C _1-4 optionally substituted) alkyl (which is especially optionally substituted Pyridyl- or pyrimidinyl- (C _1-4 ) alkyl), optionally substituted aryl (C _2-4 ) alkenyl (especially optionally substituted phenylethenyl), optionally substituted heteroaryl (C _{2- 4} ) Alkenyl (especially optionally substituted pyridylethenyl or pyrimidinylethenyl), optionally substituted aryl (C _1-4 ) alkoxy (especially optionally substituted benzyloxy and phenethyloxy), optionally substituted hetero aryl (C _1-4) alkoxy (especially optionally substituted pyridyl (C _1-4) alkoxy or pyrimidinyl (C _1-4) a Kokishi), optionally substituted aryloxy (C _1-4) alkyl (especially phenoxymethyl), optionally substituted heteroaryloxy - (C _1-4) alkyl (especially optionally substituted pyridyloxy or pyrimidinyl Oxy (C _1-4 ) alkyl), optionally substituted —S (O) _m (C _1-4 ) alkylaryl, wherein m is 0, 1 or 2 (especially optionally substituted) Benzylthio and phenethylthio), optionally substituted —S (O) _m (C _1-4 ) alkylheteroaryl, wherein m is 0, 1 or 2 (especially optionally substituted pyridyl (C _1-4) alkylthio or pyrimidinyl (C _1-4) alkylthio), optionally substituted - (C _1-4) alkyl S (O) _m aryl (wherein, m is 0, 1 or 2) ( Especially phenylthiomethyl), optionally substituted -(C _1-4 ) alkyl S (O) _m heteroaryl wherein m is 0, 1 or 2 (especially optionally substituted pyridylthio (C _1-4 ) alkyl or pyrimidinylthio ( C _1-4 ) alkyl), acyloxy including C _1-4 alkanoyloxy (especially acetyloxy) and benzoyloxy, cyano, isocyano, thiocyanato, isothiocyanato, nitro, NR ^g R ^h , —NHCOR ^g , —NHCONR ^g R ^h , -CONR ^g R ^h , -CO ₂ R ^g , -SO ₂ R ⁱ , -OSO ₂ R ⁱ , -COR ^g , -CR ^g = NR ^h , or -N = CR ^g R ^h (where R ⁱ Is C _1-4 alkyl, halo (C _1-4 ) alkyl, C _1-4 alkoxy, halo (C _1-4 ) alkoxy, C _1-4 alkylthio, C _3-6 cycloalkyl, C _3-6 cyclo Alkyl (C _1-4 ) alkyl, phenyl or The phenyl and benzyl groups are optionally substituted with halogen, C _1-4 alkyl or C _1-4 alkoxy, and R ^g and R ^h are independently hydrogen, C _1-4 alkyl, Halo (C _1-4 ) alkyl, C _1-4 alkoxy, halo (C _1-4 ) alkoxy, C _1-4 alkylthio, C _3-6 cycloalkyl, C _3-6 cyclo-alkyl (C _1-4 ) Alkyl, phenyl or benzyl, where the phenyl and benzyl groups are optionally substituted with halogen, C _1-4 alkyl, or C _1-4 alkoxy. ).

Of particular interest are compounds of formula (I) wherein Q ² is hydrogen and Q ¹ and Q ³ are as previously described.
Another group of preferred compounds of the formula (I) are those, wherein Q ¹ is halogen, aryl or heteroaryl, Q ² is hydrogen and Q ³ is as previously described.
Another group of preferred compounds of the formula (I) are those, wherein Q ¹ is aryl, Q ² is hydrogen and Q ³ is as defined above.

Another group of preferred compounds of the formula (I) are those, wherein Q ¹ is heteroaryl, Q ² is hydrogen and Q ³ is as defined above.
Another group of preferred compounds of the formula (I) are those, wherein Q ¹ and Q ³ are halogen and Q ² is hydrogen.
Another group of preferred compounds of the formula (I) are those, wherein Q ¹ is aryl or heteroaryl, Q ² is hydrogen and Q ³ is halogen.

Another group of preferred compounds of the formula (I) are those, wherein Q ¹ and Q ² are hydrogen and Q ³ is halogen or optionally substituted alkyl.
Another group of preferred compounds of the formula (I) are those, wherein Q ¹ is halogen, Q ² is hydrogen and Q ³ is optionally substituted alkyl.
Another group of preferred compounds of the formula (I) are those, wherein Q ¹ and Q ² are halogen and Q ³ is optionally substituted alkyl.

Another group of preferred compounds of the formula (I) are those, wherein Q ¹ is bromo.
Another group of preferred compounds of the formula (I) are those, wherein Q ¹ is iodo.
Another group of preferred compounds of the formula (I) are those, wherein Q ¹ is chloro.
Another group of preferred compounds of the formula (I) are those, wherein Q ¹ is fluoro.
Another group of preferred compounds of the formula (I) are those, wherein Q ³ is halogen.
Another group of preferred compounds of the formula (I) are those, wherein Q ³ is fluorine.

Another group of preferred compounds of the formula (I) are those, wherein Q ¹ is bromo, Q ² is hydrogen and Q ³ is fluoro.
Another group of preferred compounds of formula (I), Q ¹ is a bromo, Q ² is hydrogen, and Q ³ is chloro, a compound.
Another group of preferred compounds of the formula (I) are those, wherein Q ¹ is iodo, Q ² is hydrogen and Q ³ is fluoro.
Another group of preferred compounds of the formula (I) are those, wherein Q ¹ is iodo, Q ² is hydrogen and Q ³ is chloro.
Another group of preferred compounds of the formula (I) are those, wherein Q ¹ is hydrogen, halogen, aryl or heteroaryl.

Another group of preferred compounds of the formula (I) are those, wherein R ¹ is C _1-4 alkyl or halo (C _1-4 ) alkyl.
Another group of preferred compounds of the formula (I) are those, wherein R ¹ is methyl.
Another group of preferred compounds of the formula (I) are those, wherein R ¹ is ethyl.

Another group of preferred compounds of the formula (I) are those, wherein R ² is hydrogen or methyl.
Another group of preferred compounds of the formula (I) are those, wherein R ² is hydrogen.
Another group of preferred compounds of the formula (I) are those, wherein Q ¹ , Q ² and Q ³ are halogen.
Another group of preferred compounds of the formula (I) are those, wherein Q ¹ is halogen, Q ² is C _1-4 alkyl, and Q ³ is halogen.

Another group of preferred compounds of the formula (I) are those, wherein Q ¹ is halogen, Q ² is C _1-4 alkyl and Q ³ is chloro.
Another group of preferred compounds of the formula (I) are those, wherein Q ¹ is halogen, Q ² is C _1-4 alkyl, and Q ³ is fluoro.
Another group of preferred compounds of the formula (I) are those, wherein Q ¹ is halogen, Q ² is methyl and Q ³ is halogen.
Another group of preferred compounds of the formula (I) are those, wherein Q ¹ is halogen, Q ² is methyl and Q ³ is chloro.

Another group of preferred compounds of the formula (I) are those, wherein Q ¹ is halogen, Q ² is methyl and Q ³ is fluoro.
Another group of preferred compounds of the formula (I) are those, wherein Q ¹ is bromo, Q ² is methyl and Q ³ is chloro.
Another group of preferred compounds of the formula (I) are those, wherein Q ¹ is bromo, Q ² is methyl and Q ³ is fluoro.

Another group of preferred compounds of the formula (I) are those, wherein Q ¹ is iodo, Q ² is methyl and Q ³ is chloro.
Another group of preferred compounds of the formula (I) are those, wherein Q ¹ is iodo, Q ² is methyl and Q ³ is fluoro.
Another group of preferred compounds of the formula (I) are those, wherein Q ¹ is halogen and Q ² and Q ³ are C _1-4 alkyl.

Another group of preferred compounds of formula (I) is that R ³ is tert-butyl, 1-halo-2-methylprop-2-yl, 1,1-dihalo-2-methylprop-2-yl, 1,1 , 1-trihalo-2-methylprop-2-yl, 1-alkoxy-2-methylprop-2-yl, 1-alkenyloxy-2-methylprop-2-yl, 1-alkynyloxy-2-methylprop-2-yl 1-cyano-2-methyl-prop-2-yl, 1-alkoxyalkoxy-2-methyl-prop-2-yl, 1-halo-3-methylbut-3-yl, 1,1-dihalo-3- Methylbut-3-yl, 1,1,1-trihalo-3-methylbut-3-yl, 1-alkoxy-3-methylbut-3-yl, 1-alkenyloxy-3-methylbut-3-yl, 1-alkynyl Xyl-3-methylbut-3-yl, 1-cyano-3-methylbut-3-yl, 2-cyanoprop-2-yl, 2-methoxycarbonylprop-2-yl or 2-methylaminocarbonylprop-2-yl 1-alkylthio-2-methylprop-2-yl, 1-alkylsulfinyl-2-methylprop-2-yl, 1-alkylsulfonyl-2-methylprop-2-yl, 2-cyano-1-alkoxyprop-2-yl , 2-methyl-1-[(E and / or Z) -hydroxyimino] -prop-2-yl, 2-methyl-1-[(E and / or Z) -alkoxyimino] -prop-2-yl Yl, 2-methyl-1-[(E and / or Z) -aryloxyimino] -prop-2-yl, 2-methyl-1-[(E and / or Z) -heteroaryl Xyimino] -prop-2-yl, 1-alkoxy-prop-2-yl, 1-halo-prop-2-yl, 3-methyl-but-1-in-3-yl, 1-alkyl-3-methyl -But-1-in-3-yl, 4-methyl-pent-2-yn-4-yl, 1-hydroxy-4-methyl-pent-2-yn-4-yl, 1-alkoxy-4-methyl -Pent-2-yn-4-yl, 1-alkoxyalkoxy-4-methyl-pent-2-yn-4-yl, 1-alkoxyalkoxyalkyl-4-methyl-pent-2-yn-4-yl, 1-cyanoalkyl-3-methylbut-3-yl and 1-haloalkyl-3-methylbut-3-yl compounds, more preferably R ³ is tert-butyl, 1-halo-2-methylprop-2- Ill, 1-full Ro-2-methylprop-2-yl, 1-methoxy-2-methylprop-2-yl, 1-ethoxy-2-methylprop-2-yl, 1-allyloxy-2-methylprop-2-yl, 1- (prop -2-ynyloxy) -2-methylprop-2-yl, 2-cyano-1-ethoxy-prop-2-yl, 2-cyano-1-methoxyprop-2-yl, 1-halo-3-methylbuta-3 -Yl, 1-fluoro-3-methylbut-3-yl, 3-methylbut-1-in-3-yl, 4-methylpent-2-in-4-yl, 5-methyl-hex-3-in-5 -Yl, 1-methoxy-4-methyl-pent-2-yn-4-yl, 1-allyloxy-4-methyl-pent-2-yn-4-yl, 1-propargyloxy-4-methyl-pent- 2-in- 4-yl, a compound that is 1-ethoxy-4-methyl-pent-2-yn-4-yl.

Another group of preferred compounds of the formula (I) is C _1-6 alkyl, wherein R ⁴ is optionally substituted by C _1-4 alkoxy- (C _1-4 ) alkoxy (C _1-4 ) alkyl. Where the alkyl group is optionally substituted by halo, mono- or di- (C _1-6 ) alkylamino or tri (C _1-4 ) alkylsilyl, or R ⁴ is benzyloxy (C _{1 -4} ) C _1-6 alkyl optionally substituted by alkyl, wherein the alkyl group is by halo, mono- or di- (C _1-6 ) alkylamino or tri (C _1-4 ) alkylsilyl or optionally substituted, or R ⁴ is C _2-6 alkenyloxy or _{-S (O) x (C 1-6} ) C 1-6 alkyl optionally substituted by alkyl, wherein x is , 0, 1 or 2 and the alkyl group is halo, mono- or Di - (C _1-6) alkylamino, -NH (C _1-4) being optionally substituted with alkyl = NOR, wherein R is a hydrogen or C _1-4 alkyl, or wherein the alkyl The group is optionally substituted by tri (C _1-4 ) alkylsilyl or R ⁴ is —CR ^UU ═NR ^VV , where R ^UU is hydrogen or C _1-6 alkyl; And R ^VV is a compound that is hydroxy or optionally substituted C _1-6 alkoxy.

Another group of preferred compounds of the formula (I) are those wherein R ⁵ represents an optionally substituted aryl and optionally substituted heteroaryl ring or moiety is halogen, cyano, nitro, azide, C _1-6 Alkyl, halo (C _1-6 ) alkyl, C _3-6 cycloalkyl, C _3-6 cycloalkyl (C _1-4 ) alkyl, C _2-6 alkenyl, halo (C _2-6 ) alkenyl, C _{2− 6} alkynyl, halo (C _2-6 ) alkynyl, C _1-6 alkoxy, halo (C _1-6 ) alkoxy, C _2-6 alkenyloxy, halo (C _2-6 ) alkenyloxy, C _2-6 alkynyloxy , Halo (C _2-6 ) alkynyloxy, aryl, aryloxy, aryl (C _1-6 ) alkyl, aryl (C _1-6 ) alkoxy, heteroaryl, heteroaryloxy, heteroaryl (C _1-6 ) alkyl , Heteroaryl (C _1-6 ) Alkoxy, —SF ₅ , —S (O) _g (C _1-4 ) alkyl, optionally substituted, where g is 0, 1 or 2, and alkyl is optionally substituted with halo. Or R ⁵ is optionally substituted with —OSO ₂ (C _1-4 ) alkyl, wherein the alkyl group is optionally substituted with halo, or R ⁵ is —CONR ^{g _{R h, -COR g, -CO 2}} R g, -R g = NR h, -NR g R h, -NR g COR h, -NR g CO 2 R h, -SO 2 NR g R h or, - Optionally substituted by NR ^g SO ₂ R ⁱ , where R ⁱ is C _1-6 alkyl optionally substituted by halogen, and R ^g and R ^h are, independently of one another, hydrogen, Or C _1-6 alkyl optionally substituted with halogen, or —CONR ^g R ^{In the case of h} or —SO ₂ NR ^g R ^h , R ^g R ^h is bonded to a 5- or 6-membered carbocycle, or sulfur, oxygen or NR ⁰ , where R ⁰ is hydrogen or any has been is C _1-6 alkyl substituted.) may form a heterocyclic ring containing a heteroatom chosen from a compound.

Another group of preferred compounds of the formula (I) is an optionally substituted aryl, optionally substituted heteroaryl or optionally substituted 5- to 8-membered ring wherein R ⁴ is halogen, cyano , Nitro, azide, C _1-6 alkyl, halo (C _1-6 ) alkyl, C _3-6 cycloalkyl, C _3-6 cycloalkyl (C _1-4 ) alkyl, C _2-6 alkenyl, halo (C _2-6 ) Alkenyl, C _2-6 alkynyl, halo (C _2-6 ) alkynyl, C _1-6 alkoxy, halo (C _1-6 ) alkoxy, C _2-6 alkenyloxy, halo (C _2-6 ) Optionally substituted by alkenyloxy, C _2-6 alkynyloxy, halo (C _2-6 ) alkynyloxy, —SF ₅ , —S (O) _x (C _1-6 ) alkyl, where x is 0, 1 or 2 and the alkyl group is optionally substituted with halo, Is R ⁴ is, -OSO ₂ (C _1-4) being optionally substituted by alkyl, wherein the alkyl group, ^{halogen, -CONR x R y, -CON (} OR x) R y, -COR x, _{^{-CO 2 R x, -CR x =}} NR y, -NR x R y, -NR x COR y, -NR x CO 2 R y, -SO 2 NR x R y, or by -NR ^X SO ₂ R ^Z Optionally substituted, wherein R ^z is C _1-8 alkyl optionally substituted with halogen, and R ^x and R ^y are, independently of one another, optionally substituted with hydrogen or halogen. A compound that is C _1-6 alkyl.

Another group of preferred compounds of formula (I) are those wherein R ⁵⁰ is halogen, hydroxy, C _1-6 alkoxy, C _2-6 alkenyl (especially allyl), C _2-6 alkynyl (especially propargyl), C _{1- 4} alkoxy (C _1-4) alkoxy, cyano, C _1-4 alkylcarbonyloxy, aminocarbonyloxy, mono- - or di (C _1-4) alkylamino - _{carbonyloxy, S (O) p (C} 1-6 ) -Alkyl (wherein p is 0, 1 or 2), triazolyl, pyrazolyl, imidazolyl, tri (C _1-4 ) -alkylsilyloxy, optionally substituted phenoxy, optionally substituted A compound that is thienyloxy, optionally substituted benzyloxy, or C _1-4 alkyl optionally substituted with optionally substituted thienylmethoxy.

Another group of preferred compounds of formula (I) is that R ⁵⁰ is halogen, hydroxy, C _1-6 alkoxy, C _1-4 alkoxy (C _1-4 ) alkoxy, cyano, C _1-4 alkylcarbonyloxy, Aminocarbonyloxy, mono- or di (C _1-4 ) alkylamino-carbonyloxy, S (O) _p (C _1-6 ) -alkyl (wherein p is 0, 1 or 2), By triazolyl, pyrazolyl, imidazolyl, tri (C _1-4 ) -alkylsilyloxy, optionally substituted phenoxy, optionally substituted thienyloxy, optionally substituted benzyloxy, or optionally substituted thienylmethoxy A compound that is optionally substituted C _3-6 cycloalkyl.

Another group of preferred compounds of formula (I) are those in which optionally substituted aryl or optionally substituted heteroaryl, wherein R ⁵⁰ is halogen, hydroxy, mercapto, C _1-4 alkyl, C _2-4 alkenyl , C _2-4 alkynyl, C _1-4 alkoxy, C _2-4 alkenyloxy, C _2-4 alkynyloxy, halo (C _1-4 ) alkyl, halo (C _1-4 ) alkoxy, C _1-4 alkylthio , Halo (C _1-4 ) -alkylthio, hydroxy (C _1-4 ) alkyl, C _1-4 alkoxy (C _1-4 ) alkyl, C _3-6 cycloalkyl, C _3-6 cycloalkyl- (C _{1 -4)} alkyl, phenoxy, benzyloxy, benzoyloxy, cyano, isocyano, thiocyanato, isothiocyanato, ^{nitro, NR p R q, NHCOR P} , -NHCONR p R q, CONR p R q, -SO 2 R 0, OSO ₂ R ⁰ , COR ^P , CR ^p = NR ^q or N = CR ^p R ^q optionally substituted, where R ⁰ is C _1-4 alkyl, halo (C _1-4 ) alkyl, C _{1 -4} alkoxy, halo (C _1-4 ) alkoxy, C _1-4 alkylthio, C _3-6 cycloalkyl, C _3-6 cycloalkyl (C _1-4 ) alkyl, phenyl or benzyl, The benzyl group is optionally substituted with halogen, C _1-4 alkyl or C _1-4 alkoxy, and R ^p and R ^q are independently hydrogen, C _1-4 alkyl, halo (C _{1- 4} ) alkyl, C _1-4 alkoxy, halo (C _1-4 ) alkoxy, C _1-4 alkylthio, C _3-6 cycloalkyl, C _3-6 cycloalkyl (C _1-4 ) alkyl, phenyl or benzyl There, the phenyl and benzyl groups are halogen, C _1-4 alkyl or C _1-4 Al Optionally substituted by alkoxy, compounds.

Another group of preferred compounds of the formula (I) are those, wherein L is oxygen.
Another group of preferred compounds of the formula (I) are those, wherein n is 0.
Another group of preferred compounds of formula (I) are the N-oxides formed by quinoline moieties in compounds of formula I.

The compounds forming part of the invention are illustrated in Tables 1 to 192 below. Melting point (mp) and / or characteristic molecular ion (eg, M ⁺ , [M + 1] ⁺ ) values, and / or spectroscopic (1H NMR) data are presented in Examples 1-5 However, biological activity is presented in Example 6.

Table 1
In the compounds of Table 1, Q ¹ is chloro, Q ² is hydrogen, Q ³ is chloro, n is 0, L is O, R ¹ is methyl, R ² and R ³ is the general formula (I) having the meaning described in the table.

Table 2
In the compounds of Table 2, Q ¹ is bromo, Q ² is hydrogen, Q ³ is chloro, n is 0, L is O, R ¹ is methyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Accordingly, Compound 1 of Table 2 is the same as Compound 1 of Table 1 except that in Compound 1 of Table 2, Q ¹ is bromo, Q ² is hydrogen, and Q ³ is chloro. Similarly, compounds 2 to 323 of Table 2 are the compounds 2 to 323 of Table 1, respectively, except that in the compounds of Table 2 Q ¹ is bromo, Q ² is hydrogen and Q ³ is chloro, respectively. Is the same.

Table 3
In the compounds of Table 3, Q ¹ is iodo, Q ² is hydrogen, Q ³ is chloro, n is 0, L is O, R ¹ is methyl, R ² and R ³ is general formula (I) having the meanings given in Table 1. Accordingly, Compound 1 of Table 3 is the same as Compound 1 of Table 1 except that in Compound 1 of Table 3, Q ¹ is iodo, Q ² is hydrogen and Q ³ is chloro. Similarly, compounds 2 to 323 of Table 3 are the compounds 2 to 323 of Table 1, respectively, except that in the compounds of Table 3 Q ¹ is iodo, Q ² is hydrogen and Q ³ is chloro, respectively. Is the same.

Table 4
In the compounds of Table 4, Q ¹ is fluoro, Q ² is hydrogen, Q ³ is chloro, n is 0, L is O, R ¹ is methyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Accordingly, Compound 1 of Table 4 is the same as Compound 1 of Table 1 except that in Compound 1 of Table 4, Q ¹ is fluoro, Q ² is hydrogen, and Q ³ is chloro. Similarly, compounds 2 to 323 of Table 4 are the compounds 2 to 323 of Table 1, respectively, except that in the compounds of Table 4 Q ¹ is fluoro, Q ² is hydrogen and Q ³ is chloro, respectively. Is the same.

Table 5
In the compounds of Table 5, Q ¹ is chloro, Q ² is hydrogen, Q ³ is fluoro, n is 0, L is O, R ¹ is methyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Accordingly, Compound 1 of Table 5 is the same as Compound 1 of Table 1 except that in Compound 1 of Table 5, Q ¹ is chloro, Q ² is hydrogen, and Q ³ is fluoro. Similarly, compounds 2 to 323 of Table 5 are respectively compounds 2 to 323 of Table 1 except that in the compounds of Table 5 Q ¹ is chloro, Q ² is hydrogen and Q ³ is fluoro. Is the same.

Table 6
In the compounds of Table 6, Q ¹ is bromo, Q ² is hydrogen, Q ³ is fluoro, n is 0, L is O, R ¹ is methyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Accordingly, Compound 1 of Table 6 is the same as Compound 1 of Table 1 except that in Compound 1 of Table 6, Q ¹ is bromo, Q ² is hydrogen, and Q ³ is fluoro. Similarly, compounds 2 to 323 of Table 6 are the compounds 2 to 323 of Table 1, respectively, except that in the compounds of Table 6 Q ¹ is bromo, Q ² is hydrogen and Q ³ is fluoro, Is the same.

Table 7
In the compounds of Table 7, Q ¹ is iodo, Q ² is hydrogen, Q ³ is fluoro, n is 0, L is O, R ¹ is methyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Accordingly, Compound 1 of Table 7 is the same as Compound 1 of Table 1 except that in Compound 1 of Table 7, Q ¹ is iodo, Q ² is hydrogen and Q ³ is fluoro. Similarly, compounds 2 to 323 of Table 7 are the compounds 2 to 323 of Table 1, respectively, except that in the compounds of Table 7 Q ¹ is iodo, Q ² is hydrogen and Q ³ is fluoro. Is the same.

Table 8
In the compounds of Table 8, Q ¹ is fluoro, Q ² is hydrogen, Q ³ is fluoro, n is 0, L is O, R ¹ is methyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Accordingly, compound 1 of Table 8 is the same as compound 1 of Table 1 except that in compound 1 of table 8, Q ¹ is fluoro, Q ² is hydrogen and Q ³ is fluoro. Similarly, compounds 2 to 323 of Table 8 are the compounds 2 to 323 of Table 1, respectively, except that in the compounds of Table 8 Q ¹ is fluoro, Q ² is hydrogen and Q ³ is fluoro, Is the same.

Table 9
In the compounds of Table 9, Q ¹ is hydrogen, Q ² is hydrogen, Q ³ is chloro, n is 0, L is O, R ¹ is methyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Accordingly, Compound 1 of Table 9 is the same as Compound 1 of Table 1 except that in Compound 1 of Table 9, Q ¹ is hydrogen, Q ² is hydrogen, and Q ³ is chloro. Similarly, compounds 2 to 323 of Table 9 are the compounds 2 to 323 of Table 1, respectively, except that in the compounds of Table 9 Q ¹ is hydrogen, Q ² is hydrogen and Q ³ is chloro, respectively. Is the same.

Table 10
In the compounds of Table 10, Q ¹ is hydrogen, Q ² is hydrogen, Q ³ is fluoro, n is 0, L is O, R ¹ is methyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Accordingly, compound 1 of Table 10 is the same as compound 1 of Table 1 except that in compound 1 of table 10, Q ¹ is hydrogen, Q ² is hydrogen and Q ³ is fluoro. Similarly, compounds 2 to 323 of Table 10 are the compounds 2 to 323 of Table 1, respectively, except that in the compounds of Table 10 Q ¹ is hydrogen, Q ² is hydrogen and Q ³ is fluoro, respectively. Is the same.

Table 11
In the compounds of Table 11, Q ¹ is hydrogen, Q ² is hydrogen, Q ³ is bromo, n is 0, L is O, R ¹ is methyl, R ² and R ³ is general formula (I) having the meanings given in Table 1. Accordingly, Compound 1 of Table 11 is the same as Compound 1 of Table 1 except that in Compound 1 of Table 11, Q ¹ is hydrogen, Q ² is hydrogen and Q ³ is bromo. Similarly, compounds 2 to 323 of Table 11 are the compounds 2 to 323 of Table 1, respectively, except that in the compounds of Table 11 Q ¹ is hydrogen, Q ² is hydrogen and Q ³ is bromo, respectively. Is the same.

Table 12
In the compounds of Table 12, Q ¹ is chloro, Q ² is hydrogen, Q ³ is methyl, n is 0, L is O, R ¹ is methyl, R ² and R ³ is general formula (I) having the meanings given in Table 1. Accordingly, Compound 1 of Table 12 is the same as Compound 1 of Table 1 except that in Compound 1 of Table 12, Q ¹ is chloro, Q ² is hydrogen, and Q ³ is methyl. Similarly, compounds 2 to 323 of Table 12 are the compounds 2 to 323 of Table 1, respectively, except that in the compounds of Table 12 Q ¹ is chloro, Q ² is hydrogen and Q ³ is methyl, respectively. Is the same.

Table 13
In the compounds of Table 13, Q ¹ is bromo, Q ² is hydrogen, Q ³ is methyl, n is 0, L is O, R ¹ is methyl, R ² and R ³ is general formula (I) having the meanings given in Table 1. Accordingly, Compound 1 of Table 13 is the same as Compound 1 of Table 1 except that in Compound 1 of Table 13, Q ¹ is bromo, Q ² is hydrogen, and Q ³ is methyl. Similarly, compounds 2 to 323 of Table 13 are the compounds 2 to 323 of Table 1, respectively, except that in the compounds of Table 13 Q ¹ is bromo, Q ² is hydrogen and Q ³ is methyl. Is the same.

Table 14
In the compounds of Table 14, Q ¹ is iodo, Q ² is hydrogen, Q ³ is methyl, n is 0, L is O, R ¹ is methyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Accordingly, Compound 1 of Table 14 is the same as Compound 1 of Table 1 except that in Compound 1 of Table 14, Q ¹ is iodo, Q ² is hydrogen, and Q ³ is methyl. Similarly, compounds 2 to 323 of Table 14 are the compounds 2 to 323 of Table 1, respectively, except that in the compounds of Table 14 Q ¹ is iodo, Q ² is hydrogen and Q ³ is methyl, respectively. Is the same.

Table 15
In the compounds of Table 15, Q ¹ is fluoro, Q ² is hydrogen, Q ³ is methyl, n is 0, L is O, R ¹ is methyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Thus, compound 1 of Table 15 is the Q ¹ in compound 1 of Table 15 is fluoro, Q ² is hydrogen, except that Q ³ is methyl, is the same as compound 1 of Table 1. Similarly, compounds 2 to 323 of Table 15 are the compounds 2 to 323 of Table 1, respectively, except that in the compounds of Table 15 Q ¹ is fluoro, Q ² is hydrogen and Q ³ is methyl. Is the same.

Table 16
In the compounds of Table 16, Q ¹ is hydrogen, Q ² is hydrogen, Q ³ is methyl, n is 0, L is O, R ¹ is methyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Accordingly, Compound 1 of Table 16 is the same as Compound 1 of Table 1 except that in Compound 1 of Table 16, Q ¹ is hydrogen, Q ² is hydrogen and Q ³ is methyl. Similarly, compounds 2 to 323 of Table 16 are the compounds 2 to 323 of Table 1, respectively, except that in the compounds of Table 16 Q ¹ is hydrogen, Q ² is hydrogen and Q ³ is methyl. Is the same.

Table 17
In the compounds of Table 17, Q ¹ is chloro, Q ² is hydrogen, Q ³ is chloro, n is 0, L is O, R ¹ is ethyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Accordingly, compound 1 of Table 17 is the compound of Table 1 except that R ¹ is ethyl, Q ¹ is chloro, Q ² is hydrogen and Q ³ is chloro in compound 1 of Table 17. Same as 1. Similarly, compounds 2 to 323 of Table 17 are the following in the compounds of Table 17 except that R ¹ is ethyl, Q ¹ is chloro, Q ² is hydrogen and Q ³ is chloro: Same as compounds 2 to 323 in Table 1.

Table 18
The compounds of Table 18 are those wherein Q ¹ is bromo, Q ² is hydrogen, Q ³ is chloro, n is 0, L is O, R ¹ is ethyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Accordingly, compound 1 of Table 18 is the compound of Table 1 except that R ¹ is ethyl, Q ¹ is bromo, Q ² is hydrogen and Q ³ is chloro in compound 1 of table 18. Same as 1. Similarly, compounds 2 to 323 of Table 18 are the following in the compounds of Table 18 except that R ¹ is ethyl, Q ¹ is bromo, Q ² is hydrogen, and Q ³ is chloro: Same as compounds 2 to 323 in Table 1.

Table 19
In the compounds of Table 19, Q ¹ is iodo, Q ² is hydrogen, Q ³ is chloro, n is 0, L is O, R ¹ is ethyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Accordingly, compound 1 of Table 19 is the compound of Table 1 except that R ¹ is ethyl, Q ¹ is iodo, Q ² is hydrogen and Q ³ is chloro in compound 1 of Table 19. Same as 1. Similarly, compounds 2 to 323 of Table 19, respectively, are the compounds of Table 19 except that R ¹ is ethyl, Q ¹ is iodo, Q ² is hydrogen, and Q ³ is chloro, Same as compounds 2 to 323 in Table 1.

Table 20
The compounds of Table 20 are those wherein Q ¹ is chloro, Q ² is hydrogen, Q ³ is fluoro, n is 0, L is O, R ¹ is ethyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Accordingly, compound 1 of Table 20 is the compound of Table 1 except that R ¹ is ethyl, Q ¹ is chloro, Q ² is hydrogen and Q ³ is fluoro in compound 1 of Table 20. Same as 1. Similarly, compounds 2 to 323 of Table 20, respectively, except that in the compounds of Table 20 R ¹ is ethyl, Q ¹ is chloro, Q ² is hydrogen and Q ³ is fluoro, Same as compounds 2 to 323 in Table 1.

Table 21
In the compounds of Table 21, Q ¹ is bromo, Q ² is hydrogen, Q ³ is fluoro, n is 0, L is O, R ¹ is ethyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Accordingly, compound 1 of Table 21 is the compound of Table 1 except that R ¹ is ethyl, Q ¹ is bromo, Q ² is hydrogen and Q ³ is fluoro in compound 1 of Table 21 Same as 1. Similarly, compounds 2 to 323 of Table 21, respectively, are the compounds of Table 21 except that R ¹ is ethyl, Q ¹ is bromo, Q ² is hydrogen and Q ³ is fluoro, Same as compounds 2 to 323 in Table 1.

Table 22
In the compounds of Table 22, Q ¹ is iodo, Q ² is hydrogen, Q ³ is fluoro, n is 0, L is O, R ¹ is ethyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Thus, compound 1 of Table 22, R ¹ is ethyl in compound 1 of Table 22, Q ¹ is iodo, Q ² is hydrogen, except that Q ³ is fluoro, the compounds in Table 1 Same as 1. Similarly, compounds 2 to 323 of Table 22 are the following in the compounds of Table 22 except that R ¹ is ethyl, Q ¹ is iodo, Q ² is hydrogen, and Q ³ is fluoro: Same as compounds 2 to 323 in Table 1.

Table 23
In the compounds of Table 23, Q ¹ is hydrogen, Q ² is hydrogen, Q ³ is chloro, n is 0, L is O, R ¹ is ethyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Therefore, compound 1 of Table 23 is the compound of Table 1 except that R ¹ is ethyl, Q ¹ is hydrogen, Q ² is hydrogen and Q ³ is chloro in compound 1 of Table 23 Same as 1. Similarly, compounds 2 to 323 of Table 23 are the same as those of Table 23 except that in the compounds of Table 23, R ¹ is ethyl, Q ¹ is hydrogen, Q ² is hydrogen, and Q ³ is chloro, Same as compounds 2 to 323 in Table 1.

Table 24
In the compounds of Table 24, Q ¹ is hydrogen, Q ² is hydrogen, Q ³ is fluoro, n is 0, L is O, R ¹ is ethyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Accordingly, compound 1 of Table 24 is the compound of Table 1 except that R ¹ is ethyl, Q ¹ is hydrogen, Q ² is hydrogen and Q ³ is fluoro in compound 1 of Table 24. Same as 1. Similarly, compounds 2 to 323 of Table 24 are the following in the compounds of Table 24 except that R ¹ is ethyl, Q ¹ is hydrogen, Q ² is hydrogen and Q ³ is fluoro: Same as compounds 2 to 323 in Table 1.

Table 25
In the compounds of Table 25, Q ¹ is chloro, Q ² is hydrogen, Q ³ is methyl, n is 0, L is O, R ¹ is ethyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Accordingly, compound 1 of Table 25 is the compound of Table 1 except that R ¹ is ethyl, Q ¹ is chloro, Q ² is hydrogen and Q ³ is methyl in compound 1 of Table 25. Same as 1. Similarly, compounds 2 to 323 of Table 25 are the following in the compounds of Table 25 except that R ¹ is ethyl, Q ¹ is chloro, Q ² is hydrogen, and Q ³ is methyl: Same as compounds 2 to 323 in Table 1.

Table 26
In the compounds of Table 26, Q ¹ is bromo, Q ² is hydrogen, Q ³ is methyl, n is 0, L is O, R ¹ is ethyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Accordingly, compound 1 of Table 26 is the compound of Table 1 except that R ¹ is ethyl, Q ¹ is bromo, Q ² is hydrogen and Q ³ is methyl in compound 1 of table 26 Same as 1. Similarly, compounds 2 to 323 of Table 26 are the following in the compounds of Table 26 except that R ¹ is ethyl, Q ¹ is bromo, Q ² is hydrogen and Q ³ is methyl: Same as compounds 2 to 323 in Table 1.

Table 27
In the compounds of Table 27, Q ¹ is iodo, Q ² is hydrogen, Q ³ is methyl, n is 0, L is O, R ¹ is ethyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Thus, compound 1 of Table 27 is the compound of Table 1 except that R ¹ is ethyl, Q ¹ is iodo, Q ² is hydrogen and Q ³ is methyl in compound 1 of table 27 Same as 1. Similarly, compounds 2 to 323 of Table 27 are the following in the compounds of Table 27 except that R ¹ is ethyl, Q ¹ is iodo, Q ² is hydrogen and Q ³ is methyl: Same as compounds 2 to 323 in Table 1.

Table 28
The compounds of Table 28 are those wherein Q ¹ is hydrogen, Q ² is hydrogen, Q ³ is methyl, n is 0, L is O, R ¹ is ethyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Accordingly, compound 1 of Table 28 is the compound of Table 1 except that R ¹ is ethyl, Q ¹ is hydrogen, Q ² is hydrogen and Q ³ is methyl in compound 1 of Table 28. Same as 1. Similarly, compounds 2 to 323 of Table 28 are the following in the compounds of Table 28 except that R ¹ is ethyl, Q ¹ is hydrogen, Q ² is hydrogen and Q ³ is methyl: Same as compounds 2 to 323 in Table 1.

Table 29
In the compounds of Table 29, Q ¹ is thiophen-3-yl, Q ² is hydrogen, Q ³ is chloro, n is 0, L is O, R ¹ is methyl, R ² and R ³ are general formula (I) having the meanings listed in Table 1. Accordingly, compound 1 of Table 29 is the same as compound 1 of Table 1 except that in compound 1 of table 29 Q ¹ is thiophen-3-yl, Q ² is hydrogen and Q ³ is chloro. It is. Similarly, compounds 2 to 323 of Table 29 are the same as those of Table 1 except that in the compounds of Table 29 Q ¹ is thiophen-3-yl, Q ² is hydrogen and Q ³ is chloro. Same as compounds 2 to 323.

Table 30
The compounds of Table 30 are those wherein Q ¹ is thiophen-3-yl, Q ² is hydrogen, Q ³ is fluoro, n is 0, L is O, R ¹ is methyl, R ² and R ³ are general formula (I) having the meanings listed in Table 1. Therefore, compound 1 of Table 30 is the same as compound 1 of Table 1 except that in compound 1 of table 30 Q ¹ is thiophen-3-yl, Q ² is hydrogen and Q ³ is fluoro. It is. Similarly, compounds 2 to 323 of Table 30 are the same as those of Table 1 except that in the compounds of Table 30, Q ¹ is thiophen-3-yl, Q ² is hydrogen, and Q ³ is fluoro. Same as compounds 2 to 323.

Table 31
The compounds of Table 31 are those wherein Q ¹ is thiophen-2-yl, Q ² is hydrogen, Q ³ is chloro, n is 0, L is O, R ¹ is methyl, R ² and R ³ are general formula (I) having the meanings listed in Table 1. Accordingly, Compound 1 of Table 31 is the same as Compound 1 of Table 1 except that in Compound 1 of Table 31, Q ¹ is thiophen-2-yl, Q ² is hydrogen, and Q ³ is chloro. It is. Similarly, compounds 2 to 323 of Table 31 are the same as those of Table 1 except that in the compounds of Table 31, Q ¹ is thiophen-2-yl, Q ² is hydrogen, and Q ³ is chloro. Same as compounds 2 to 323.

Table 32
In the compounds of Table 32, Q ¹ is thiophen-2-yl, Q ² is hydrogen, Q ³ is fluoro, n is 0, L is O, R ¹ is methyl, R ² and R ³ are general formula (I) having the meanings listed in Table 1. Accordingly, Compound 1 of Table 32 is the same as Compound 1 of Table 1 except that in Compound 1 of Table 32, Q ¹ is thiophen-2-yl, Q ² is hydrogen, and Q ³ is fluoro. It is. Similarly, compounds 2 to 323 of Table 32 are the same as those of Table 1 except that in the compounds of Table 32, Q ¹ is thiophen-2-yl, Q ² is hydrogen, and Q ³ is fluoro. Same as compounds 2 to 323.

Table 33
In the compounds of Table 33, Q ¹ is thiophen-3-yl, Q ² is hydrogen, Q ³ is chloro, n is 0, L is O, R ¹ is ethyl, R ² and R ³ are general formula (I) having the meanings listed in Table 1. Accordingly, Compound 1 of Table 33 is the same as Compound 1 of Table 1 except that in Compound 1 of Table 33, Q ¹ is thiophen-3-yl, Q ² is hydrogen, and Q ³ is chloro. It is. Similarly, compounds 2 to 323 of Table 33 are the same as those of Table 1 except that in the compounds of Table 32, Q ¹ is thiophen-3-yl, Q ² is hydrogen, and Q ³ is chloro. Same as compounds 2 to 323.

Table 34
In the compounds of Table 34, Q ¹ is thiophen-3-yl, Q ² is hydrogen, Q ³ is fluoro, n is 0, L is O, R ¹ is ethyl, R ² and R ³ are general formula (I) having the meanings listed in Table 1. Accordingly, Compound 1 of Table 34 is the same as Compound 1 of Table 1 except that in Compound 1 of Table 34 Q ¹ is thiophen-3-yl, Q ² is hydrogen and Q ³ is fluoro. It is. Similarly, compounds 2 to 323 of Table 34 are the compounds of Table 1 except that in the compounds of Table 34, Q ¹ is thiophen-3-yl, Q ² is hydrogen, and Q ³ is fluoro. Same as compounds 2 to 323.

Table 35
The compounds of Table 35 have Q ¹ is thiophen-2-yl, Q ² is hydrogen, Q ³ is chloro, n is 0, L is O, R ¹ is ethyl, R ² and R ³ are general formula (I) having the meanings listed in Table 1. Thus, compound 1 of Table 35, Q ¹ in compound 1 of Table 35 is thiophene-2-yl, Q ² is hydrogen, except that Q ³ is chloro, same as compound 1 of Table 1 It is. Similarly, compounds 2 to 323 of Table 35 are each of the compounds in Table 1 except that in the compounds of Table 35 Q ¹ is thiophen-2-yl, Q ² is hydrogen and Q ³ is chloro. Same as compounds 2 to 323.

Table 36
The compounds of Table 36 have Q ¹ is thiophen-2-yl, Q ² is hydrogen, Q ³ is fluoro, n is 0, L is O, R ¹ is ethyl, R ² and R ³ are general formula (I) having the meanings listed in Table 1. Accordingly, Compound 1 of Table 36 is the same as Compound 1 of Table 1 except that in Compound 1 of Table 36 Q ¹ is thiophen-2-yl, Q ² is hydrogen and Q ³ is fluoro. It is. Similarly, compounds 2 to 323 of Table 36 are the same as those of Table 1 except that in the compounds of Table 36, Q ¹ is thiophen-2-yl, Q ² is hydrogen, and Q ³ is fluoro. Same as compounds 2 to 323.

Table 37
The compounds of Table 37 have Q ¹ is chloro, Q ² is methyl, Q ³ is chloro, n is 0, L is O, R ¹ is methyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Accordingly, Compound 1 of Table 37 is the same as Compound 1 of Table 1 except that in Compound 1 of Table 37, Q ¹ is chloro, Q ² is methyl, and Q ³ is chloro. Similarly, compounds 2 to 323 of Table 37 are the compounds 2 to 323 of Table 1, respectively, except that in the compounds of Table 37 Q ¹ is chloro, Q ² is methyl and Q ³ is chloro, respectively. Is the same.

Table 38
The compounds of Table 38 have Q ¹ is bromo, Q ² is methyl, Q ³ is chloro, n is 0, L is O, R ¹ is methyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Accordingly, Compound 1 of Table 38 is the same as Compound 1 of Table 1 except that in Compound 1 of Table 38, Q ¹ is bromo, Q ² is methyl, and Q ³ is chloro. Similarly, compounds 2 to 323 of Table 38 are the compounds 2 to 323 of Table 1, respectively, except that in the compounds of Table 38 Q ¹ is bromo, Q ² is methyl and Q ³ is chloro, respectively. Is the same.

Table 39
In the compounds of Table 39, Q ¹ is iodo, Q ² is methyl, Q ³ is chloro, n is 0, L is O, R ¹ is methyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Accordingly, compound 1 of Table 39 is the same as compound 1 of Table 1 except that in compound 1 of table 39 Q ¹ is iodo, Q ² is methyl and Q ³ is chloro. Similarly, compounds 2 to 323 of Table 39 are the compounds 2 to 323 of Table 1, respectively, except that in the compounds of Table 39 Q ¹ is iodo, Q ² is methyl and Q ³ is chloro, respectively. Is the same.

Table 40
In the compounds of Table 40, Q ¹ is fluoro, Q ² is methyl, Q ³ is chloro, n is 0, L is O, R ¹ is methyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Accordingly, Compound 1 of Table 40 is the same as Compound 1 of Table 1 except that in Compound 1 of Table 40, Q ¹ is fluoro, Q ² is methyl, and Q ³ is chloro. Similarly, compounds 2 to 323 of Table 40 are the compounds 2 to 323 of Table 1, respectively, except that in the compounds of Table 40 Q ¹ is fluoro, Q ² is methyl and Q ³ is chloro, respectively. Is the same.

Table 41
In the compounds of Table 41, Q ¹ is chloro, Q ² is methyl, Q ³ is fluoro, n is 0, L is O, R ¹ is methyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Accordingly, compound 1 of Table 41 is the same as compound 1 of Table 1 except that in compound 1 of table 41 Q ¹ is chloro, Q ² is methyl and Q ³ is fluoro. Similarly, compounds 2 to 323 of Table 41 are the compounds 2 to 323 of Table 1, respectively, except that in the compounds of Table 41 Q ¹ is chloro, Q ² is methyl and Q ³ is fluoro, Is the same.

Table 42
In the compounds of Table 42, Q ¹ is bromo, Q ² is methyl, Q ³ is fluoro, n is 0, L is O, R ¹ is methyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Accordingly, Compound 1 of Table 42 is the same as Compound 1 of Table 1 except that in Compound 1 of Table 42, Q ¹ is bromo, Q ² is methyl, and Q ³ is fluoro. Similarly, compounds 2 to 323 of Table 42 are the compounds 2 to 323 of Table 1 respectively except that in the compounds of Table 42 Q ¹ is bromo, Q ² is methyl and Q ³ is fluoro. Is the same.

Table 43
In the compounds of Table 43, Q ¹ is iodo, Q ² is methyl, Q ³ is fluoro, n is 0, L is O, R ¹ is methyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Accordingly, Compound 1 of Table 43 is the same as Compound 1 of Table 1 except that in Compound 1 of Table 43, Q ¹ is iodo, Q ² is methyl and Q ³ is fluoro. Similarly, compounds 2 to 323 of Table 43 are the compounds 2 to 323 of Table 1, respectively, except that in the compounds of Table 43 Q ¹ is iodo, Q ² is methyl and Q ³ is fluoro, Is the same.

Table 44
In the compounds of Table 44, Q ¹ is fluoro, Q ² is methyl, Q ³ is fluoro, n is 0, L is O, R ¹ is methyl, R ² and R ³ is general formula (I) having the meanings given in Table 1. Accordingly, Compound 1 of Table 44 is the same as Compound 1 of Table 1 except that in Compound 1 of Table 44, Q ¹ is fluoro, Q ² is methyl, and Q ³ is fluoro. Similarly, compounds 2 to 323 of Table 44 are the compounds 2 to 323 of Table 1 respectively except that in the compounds of Table 44 Q ¹ is fluoro, Q ² is methyl and Q ³ is fluoro. Is the same.

Table 45
The compounds of Table 45 have Q ¹ is chloro, Q ² is methyl, Q ³ is bromo, n is 0, L is O, R ¹ is methyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Accordingly, Compound 1 of Table 45 is the same as Compound 1 of Table 1 except that in Compound 1 of Table 45, Q ¹ is chloro, Q ² is methyl, and Q ³ is bromo. Similarly, compounds 2 to 323 of Table 45 are the compounds 2 to 323 of Table 1, respectively, except that in the compounds of Table 45 Q ¹ is chloro, Q ² is methyl and Q ³ is bromo, respectively. Is the same.

Table 46
The compounds of Table 46 have Q ¹ is bromo, Q ² is methyl, Q ³ is bromo, n is 0, L is O, R ¹ is methyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Thus, compound 1 of Table 46, Q ¹ in compound 1 of Table 46 is bromo, Q ² is methyl, except that Q ³ is bromo, is the same as compound 1 of Table 1. Similarly, compounds 2 to 323 of Table 46 are the compounds 2 to 323 of Table 1 respectively except that in the compounds of Table 46 Q ¹ is bromo, Q ² is methyl and Q ³ is bromo. Is the same.

Table 47
In the compounds of Table 47, Q ¹ is iodo, Q ² is methyl, Q ³ is bromo, n is 0, L is O, R ¹ is methyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Accordingly, Compound 1 of Table 47 is the same as Compound 1 of Table 1 except that in Compound 1 of Table 47 Q ¹ is iodo, Q ² is methyl and Q ³ is bromo. Similarly, compounds 2 to 323 of Table 47 are the compounds 2 to 323 of Table 1, respectively, except that in the compounds of Table 47 Q ¹ is iodo, Q ² is methyl and Q ³ is bromo, respectively. Is the same.

Table 48
The compounds of Table 48 are those where Q ¹ is fluoro, Q ² is methyl, Q ³ is bromo, n is 0, L is O, R ¹ is methyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Accordingly, Compound 1 of Table 48 is the same as Compound 1 of Table 1 except that in Compound 1 of Table 48, Q ¹ is fluoro, Q ² is methyl, and Q ³ is bromo. Similarly, compounds 2 to 323 of Table 48 are the compounds 2 to 323 of Table 1 respectively except that in the compounds of Table 48 Q ¹ is fluoro, Q ² is methyl and Q ³ is bromo. Is the same.

Table 49
The compounds of Table 49 have Q ¹ is chloro, Q ² is chloro, Q ³ is fluoro, n is 0, L is O, R ¹ is methyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Accordingly, compound 1 of Table 49 is the same as compound 1 of Table 1 except that in compound 1 of table 49 Q ¹ is chloro, Q ² is chloro and Q ³ is fluoro. Similarly, compounds 2 to 323 of Table 49 are the compounds 2 to 323 of Table 1, respectively, except that in the compounds of Table 49 Q ¹ is chloro, Q ² is chloro and Q ³ is fluoro, Is the same.

Table 50
The compounds in Table 50 have Q ¹ is bromo, Q ² is chloro, Q ³ is fluoro, n is 0, L is O, R ¹ is methyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Accordingly, compound 1 of Table 50 is the same as compound 1 of Table 1 except that in compound 1 of table 50 Q ¹ is bromo, Q ² is chloro and Q ³ is fluoro. Similarly, compounds 2 to 323 of Table 50 are the Q ¹ is bromo in the compounds of Table 50, Q ² is chloro, except Q ³ is fluoro, respectively, from the compound 2 in Table 1 323 Is the same.

Table 51
The compounds of Table 51 are those wherein Q ¹ is fluoro, Q ² is chloro, Q ³ is fluoro, n is 0, L is O, R ¹ is methyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Accordingly, Compound 1 of Table 51 is the same as Compound 1 of Table 1 except that in Compound 1 of Table 51 Q ¹ is fluoro, Q ² is chloro and Q ³ is fluoro. Similarly, compounds 2 to 323 of Table 51 are the compounds 2 to 323 of Table 1, respectively, except that in the compounds of Table 51 Q ¹ is fluoro, Q ² is chloro and Q ³ is fluoro, Is the same.

Table 52
The compounds of Table 52 have Q ¹ is iodo, Q ² is chloro, Q ³ is fluoro, n is 0, L is O, R ¹ is methyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Accordingly, Compound 1 of Table 52 is the same as Compound 1 of Table 1 except that in Compound 1 of Table 52 Q ¹ is iodo, Q ² is chloro and Q ³ is fluoro. Similarly, compounds 2 to 323 of Table 52 are the compounds 2 to 323 of Table 1 respectively except that in the compounds of Table 52 Q ¹ is iodo, Q ² is chloro and Q ³ is fluoro. Is the same.

Table 53
The compounds of Table 53 have Q ¹ is chloro, Q ² is bromo, Q ³ is fluoro, n is 0, L is O, R ¹ is methyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Accordingly, Compound 1 of Table 53 is the same as Compound 1 of Table 1 except that in Compound 1 of Table 53 Q ¹ is chloro, Q ² is bromo and Q ³ is fluoro. Similarly, compounds 2 to 323 of Table 53 are the compounds 2 to 323 of Table 1, respectively, except that in the compounds of Table 53 Q ¹ is chloro, Q ² is bromo and Q ³ is fluoro, respectively. Is the same.

Table 54
The compounds of Table 54 have Q ¹ is bromo, Q ² is bromo, Q ³ is fluoro, n is 0, L is O, R ¹ is methyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Accordingly, Compound 1 of Table 54 is the same as Compound 1 of Table 1 except that in Compound 1 of Table 54, Q ¹ is bromo, Q ² is bromo and Q ³ is fluoro. Similarly, compounds 2 to 323 of Table 54 are the compounds 2 to 323 of Table 1, respectively, except that in the compounds of Table 54 Q ¹ is bromo, Q ² is bromo and Q ³ is fluoro, respectively. Is the same.

Table 55
The compounds of Table 55 are those where Q ¹ is fluoro, Q ² is bromo, Q ³ is fluoro, n is 0, L is O, R ¹ is methyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Accordingly, Compound 1 of Table 55 is the same as Compound 1 of Table 1 except that in Compound 1 of Table 55, Q ¹ is fluoro, Q ² is bromo, and Q ³ is fluoro. Similarly, compounds 2 to 323 of Table 55 are the compounds 2 to 323 of Table 1 respectively except that in the compounds of Table 55 Q ¹ is fluoro, Q ² is bromo and Q ³ is fluoro. Is the same.

Table 56
The compounds of Table 56 have Q ¹ is iodo, Q ² is bromo, Q ³ is fluoro, n is 0, L is O, R ¹ is methyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Accordingly, Compound 1 of Table 56 is the same as Compound 1 of Table 1 except that in Compound 1 of Table 56 Q ¹ is iodo, Q ² is bromo and Q ³ is fluoro. Similarly, compounds 2 to 323 of Table 56 are the compounds 2 to 323 of Table 1 respectively except that in the compounds of Table 56 Q ¹ is iodo, Q ² is bromo and Q ³ is fluoro. Is the same.

Table 57
The compounds of Table 57, Q ¹ is chloro, Q ² is fluoro, Q ³ is fluoro, n is 0, L is O, R ¹ is methyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Accordingly, Compound 1 of Table 57 is the same as Compound 1 of Table 1 except that in Compound 1 of Table 57, Q ¹ is chloro, Q ² is fluoro, and Q ³ is fluoro. Similarly, compounds 2 to 323 of Table 57 are the compounds 2 to 323 of Table 1, respectively, except that in the compounds of Table 57 Q ¹ is chloro, Q ² is fluoro and Q ³ is fluoro, Is the same.

Table 58
The compounds of Table 58 have the compounds wherein Q ¹ is bromo, Q ² is fluoro, Q ³ is fluoro, n is 0, L is O, R ¹ is methyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Accordingly, Compound 1 of Table 58 is the same as Compound 1 of Table 1 except that in Compound 1 of Table 58, Q ¹ is bromo, Q ² is fluoro, and Q ³ is fluoro. Similarly, compounds 2 to 323 of Table 58 are the compounds 2 to 323 of Table 1 respectively except that in the compounds of Table 58 Q ¹ is bromo, Q ² is fluoro and Q ³ is fluoro, respectively. Is the same.

Table 59
The compounds of Table 59 have the compounds wherein Q ¹ is fluoro, Q ² is fluoro, Q ³ is fluoro, n is 0, L is O, R ¹ is methyl, R ² and R ³ is general formula (I) having the meanings given in Table 1. Accordingly, Compound 1 of Table 59 is the same as Compound 1 of Table 1 except that in Compound 1 of Table 59, Q ¹ is fluoro, Q ² is fluoro, and Q ³ is fluoro. Similarly, compounds 2 to 323 of Table 59 are the compounds 2 to 323 of Table 1 respectively except that in the compounds of Table 59 Q ¹ is fluoro, Q ² is fluoro and Q ³ is fluoro. Is the same.

Table 60
The compounds of Table 60 are those wherein Q ¹ is iodo, Q ² is fluoro, Q ³ is fluoro, n is 0, L is O, R ¹ is methyl, R ² and R ³ is the general formula (I) having the meaning described in Table 1. Accordingly, Compound 1 of Table 60 is the same as Compound 1 of Table 1 except that in Compound 1 of Table 60, Q ¹ is iodo, Q ² is fluoro, and Q ³ is fluoro. Similarly, compounds 2 to 323 of Table 60 are the compounds 2 to 323 of Table 1, respectively, except that in the compounds of Table 60 Q ¹ is iodo, Q ² is fluoro and Q ³ is fluoro, respectively. Is the same.

Table 61
In the compounds of Table 61, Q ¹ is thiophen-3-yl, Q ² is fluoro, Q ³ is fluoro, n is 0, L is O, R ¹ is methyl, R ² and R ³ are general formula (I) having the meanings listed in Table 1. Accordingly, compound 1 of Table 61 is the same as compound 1 of Table 1 except that in compound 1 of table 61 Q ¹ is thiophen-3-yl, Q ² is fluoro and Q ³ is fluoro. It is. Similarly, compounds 2 to 323 of Table 61 are the same as those of Table 1 except that in the compounds of Table 61, Q ¹ is thiophen-3-yl, Q ² is fluoro, and Q ³ is fluoro. Same as compounds 2 to 323.

Tables 62 to 121
Tables 62 to 121 correspond exactly to Tables 1 to 61 (ie, Table 62 corresponds exactly to Table 1, Table 63 corresponds exactly to Table 2, etc.), the only difference In each of Tables 62 to 121, L is S instead of O.

Table 122 to 181
Tables 122 to 181 correspond exactly to Tables 1 to 61 (ie, Table 122 corresponds exactly to Table 1, Table 123 corresponds exactly to Table 2, etc.), the only difference In each of Tables 122 to 181, n is 1 instead of 0.

Tables 182 to 241
Tables 182 to 241 correspond exactly to Tables 1 to 61 (ie, Table 182 corresponds exactly to Table 1, Table 183 corresponds exactly to Table 2, etc.), the only difference In each of Tables 182-141, n is 2 instead of 0.

The compounds of general formula (I) may be prepared as outlined in Schemes 1 to 8 below, where Q ¹ , Q ² , Q ³ , R ¹ , R ² and R ³ are as previously indicated. R ¹⁴ is H or C _1-4 alkyl, as indicated, and R ¹⁰ is C _1-6 alkyl, optionally substituted benzyl, optionally substituted C 1 _2-6 alkenyl, optionally substituted C _2-4 alkynyl, R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹² and R ¹³ are independently H or C _1-4 alkyl; R ^g is H or C _1-3 alkyl, R ^h is H or C _1-3 alkyl, R ⁱ is C _1-6 alkyl, optionally substituted benzyl, optionally substituted C _2-6 alkenyl, C _2-4 alkynyl optionally substituted, m is 0, 1 or 2, DMF is, N, an N- dimethylformamide, NBS is N A bromosuccinimide, NCS is N- chlorosuccinimide and MCPBA is m- chloroperbenzoic acid. Other abbreviations are defined below.

  Where typical or preferred processing conditions (reaction temperature, time, solvent, reactant molecular ratio) are given, other processing conditions may be used unless otherwise specified. Optimum reaction conditions may vary with the particular reactants or solvent used, but such conditions can be determined by routine optimization procedures by one skilled in the art.

Compounds of formula (1), where n is 0 and L is O, may be prepared as shown in Scheme 1. Esters of formula (2) in which R ⁵ is C _1-4 alkyl are radical reactions such as AIBN (azo-isobutyronitrile) in a suitable solvent such as carbon tetrachloride or acetonitrile. Halogenated by reaction with a halogenating agent such as N-bromosuccinimide between the ambient temperature and the reflux temperature of the solvent in the presence of an initiator and a light source to form a haloester of formula (3) , Hal is a halogen atom such as bromine, chlorine or iodine). The compound of general formula (3) is then reacted with an alkanethiol of general formula R ¹ SH in a suitable solvent such as DMF in the presence of a base such as sodium hydride. Or reacting with an alkanethiol salt R ¹ S ⁻ M ⁺ (wherein M is a metal such as sodium or lithium) in a suitable solvent such as DMF to produce a compound of general formula (6) This yields a compound.

Alternatively, the ester of general formula (4) is a halogen such as N-chlorosuccinimide or N-bromosuccinimide between 0 ° C. and the reflux temperature of the solvent in a suitable solvent such as carbon tetrachloride or acetonitrile. Upon reaction with the agent, it is halogenated to give a haloester of formula (5), where Hal is a halogen atom such as bromine, chlorine or iodine. The haloester of formula (5) is 6-hydroxyquinoline (wherein Q ¹ , Q ² and Q ³ are as defined above), t-butanol, 1,4-dioxane or DMF, etc. In a suitable solvent, in the presence of a base such as potassium t-butoxide, potassium carbonate or sodium hydride, between ambient temperature and the reflux temperature of the solvent to give a compound of formula (6). The compound of formula (6) can be reacted with an alkali metal hydroxide M ⁺ OH ^{− in} a suitable solvent such as aqueous methanol, ethanol or THF (tetrahydrofuran) between ambient temperature and the reflux temperature of the solvent. Hydrolysis to the acid of formula (7) by reaction and subsequent acidification. The acid of formula (7) uses a suitable activator such as HOBT (1-hydroxybenzotriazole) and EDC (1-ethyl-3-N, N-dimethylaminopropylcarbodiimide hydrochloride), such as DMF. Condensation with an amine of formula (8) between 0 ° C. and ambient temperature in a suitable solvent, yielding a compound of general formula (1), wherein n is 0 and L is O .

As shown in Scheme 2, the compound of formula (1) (wherein n is 1 or 2) is converted into a sulfoxide (n is 1) by oxidation of compound (1) (where n = 0). Or sulfone (n is 2) in the oxidation state. For example, an ester of general formula (6) (wherein R ⁵ is C _1-4 alkyl) can be reacted with an oxidizing agent such as sodium periodate in a suitable solvent such as ethanol at 0 ° C. and ambient temperature. In between can be oxidized to the sulfoxide of formula (9). The sulfone of formula (10) is obtained from the compound of formula (6) in a suitable solvent such as dichloromethane between 0 ° C. and the reflux temperature of the solvent, 2 equivalents or more of m-chloro-perbenzoic acid. It can be produced either directly with an oxidizing agent such as (MCPBA) or from sulfoxide of formula (9) with one equivalent or more of m-chloroperbenzoic acid. The sulfide of formula (6), the sulfoxide of formula (9) or the sulfone of formula (10) is an alkali metal hydroxide between 0 ° C. and the reflux temperature of the solvent in a suitable solvent such as ethanol. Can be hydrolyzed to the corresponding acid (7), (11) or (12) by reaction with The acid of formula (7), (11) or (12) is condensed with an amine of formula (8) between 0 ° C. and ambient temperature using suitable activators such as HOBT and EDC, This yields a compound of formula (1), where n is 0, 1 or 2.

  Similarly, the sulfoxides of formula (11) and formula (1) (where n is 1) are of formula (7) and formula (1) (where n is 0), respectively. It can be prepared from sulfide using sodium metaperiodate or m-chloroperbenzoic acid as described above. The sulfone of formula (12) and formula (1) (where n is 2) is at least 2 from the sulfides of formula (7) and formula (1) (where n is 0). From sulfoxides of formula (11) and formula (1) (where n is 1) by using an equivalent of an oxidizing agent such as m-chloroperbenzoic acid, as described above, 1 It can be prepared either by using an equivalent or more oxidizing agent such as m-chloroperbenzoic acid.

Compounds of formula (1) can also be prepared as shown in Scheme 3. The acid of formula (13) is condensed between 0 ° C. and ambient temperature using an amine of formula (8) and a suitable activator such as HOBT and EDC to give the compound of formula (14). The compound of formula (14) is halogenated to a compound of formula (16) between 0 ° C. and ambient temperature in a suitable solvent such as carbon tetrachloride or acetonitrile using a halogenating agent such as N-chlorosuccinimide. Can be The amide of formula (16) is obtained from an acid halide of formula (15) in the presence of a base such as triethylamine in a suitable solvent such as dichloromethane between 0 ° C. and ambient temperature. It can be prepared by reacting with.

  The halosulfide of formula (16) reacts with a substituted 6-hydroxyquinoline in the presence of a base such as potassium carbonate or sodium hydride in a suitable solvent such as DMF at 0-80 ° C. 1) (wherein n is 0).

As shown in Scheme 4, the amine of general formula (18) or (20), which is an example of an amine of general formula (8) (wherein R ² is H), Alkylation of the amino alcohol of 17) or (19) using a suitable base such as n-butyllithium or sodium hydride followed by a suitable alkylating agent R ¹⁰ LG, for example iodide such as methyl iodide It may be prepared by reaction with alkyl to form an alkylated compound of general formula (18) or (20). For example, carbonyl derivatives R ¹² COR ¹³ (21), such as formaldehyde, can react with ammonia, usually in the form of ammonium chloride, and conveniently cyanide in the form of aqueous sodium cyanide, and α-aminoalkyne ( 22) (Strecker synthesis).

As shown in Scheme 5, the silyl-protected aminoalkyne of general formula (24) is an amine of general formula (23) in the presence of a suitable base such as a tertiary organic amine base, for example triethylamine. Can be obtained by reaction with 1,2-bis- (chlorodimethylsilyl) -ethane. Examples of amines of general formula (8) (wherein R ² is H and R ³ is — (CR ³⁰ R ⁴⁰ ) C≡CR ⁵⁰ ). Alkylation of a silyl-protected aminoalkyne of formula (24) using a suitable base such as n-butyllithium followed by a suitable alkylating agent R ⁵⁰ LG, for example an alkyl iodide such as methyl iodide and To form an alkylated compound of general formula (25). The silyl protecting group can then be removed to form a compound of general formula (25), for example, an aminoalkyne of general formula (26) is formed with an aqueous acid solution.

In a similar procedure, a silyl-protected aminoalkyne of general formula (24) is reacted with ^a carbonyl derivative R ^a COR ^b , eg formaldehyde, using a suitable base such as n-butyllithium and containing a hydroxyalkyl moiety. Aminoalkyne (27) may be provided. The compound of general formula (27) is first treated with a base such as sodium hydride or potassium bis (trimethylsilyl) amide and then treated with compound R ^c LG (where LG represents a leaving group such as halogen), Or may be treated with a sulfonate ester such as OSO ₂ Me, or OSO ₂ -4-tolyl such as ethyl iodide to yield a compound of general formula (29). After removal of the silyl protecting group, the compound of general formula (30) is obtained. Alternatively, the silyl protecting group can be removed first to give a compound of general formula (28). The aminoalkyne of general formula (28) may be further derivatized by reaction with a silylating agent such as t-butyl-dimethylsilyl chloride to yield a derivative of oxygen of general formula (31).

As shown in Scheme 6, silyl-protected aminoalkynes of general formula (32) have silyl-protected amines of general formula (24) with suitable leaving groups such as bromide or iodide. It can be obtained by reacting a chloroalkane with a suitable base such as sodium or lithium amide base, for example sodium bis (trimethylsilyl) amide or sodium amide. Examples of amines of general formula (8) are amines of general formula (34) wherein R ² is H and R ³ is — (CR ³⁰ R ⁴⁰ ) C≡CR ^50. It may be prepared by replacing the anion with a cyanide followed by removal of the silyl protecting group, for example with an aqueous acid solution, to form the cyano compound of general formula (34).
In a similar procedure, an amide of general formula (35) can be reacted with, for example, potassium cyanide to give a cyanoamidoalkyne of general formula (36).

As shown in Scheme 7, compounds of general formula (1) (wherein R ⁵⁰ is H) can, for example, be optionally substituted aryl or heteroaryl chloride, bromide, It may react with iodide or triflate to form a substituted aryl or heteroaryl compound of general formula (1), wherein R ⁵⁰ is an optionally substituted aryl or heteroaryl group. A preferred palladium catalyst is bis (triphenylphosphine) palladium (II) chloride.

Other amines of general formula (8) are either commercially available or may be prepared by standard literature methods or standard modifications.
As shown in Scheme 8, compounds of general formula (1) (wherein Q ¹ is bromine or iodine) can be obtained under Suzuki conditions, for example, optionally substituted arylboronic acids or heteroarylboronic acids. To form a substituted aryl or heteroaryl compound of general formula (1), wherein Q ¹ is an optionally substituted aryl or heteroaryl group. A suitable palladium catalyst is tetrakis (triphenylphosphine) palladium (0).

  Thioamides (compounds of general formula (1) where L = S) are prepared from the corresponding amides using sulfiding agents such as phosphorus pentasulfide, Ravensson's reagent or Debi's reagent, or the corresponding thionoic acid ( thionoacid) or thionoesters using standard literature methods or standard modifications.

  Substituted 6-hydroxyquinolines are available or may be prepared using straightforward techniques of organic chemistry. If these compounds are not commercially available, they may be prepared from available precursors using simple and clear transformations well known in the art well-described in standard textbooks on heterocyclic chemistry. Good. For example, a substituted aromatic amine can be readily converted to a substituted quinolin-6-ol by a suitable electrophile such as 2,2,3-tribromopropanal. Examples of such reactions are presented in Examples 1 to 3.

  The compounds of formula (I) are active fungicides and may be used to control one or more of the following pathogens: Pyricularia oryzae (rice blast fungus on rice and wheat) (Magnaporthe grisea) and other Pyricularia species for other hosts; Puccinia triticina (or Puccinia recondita), Puccinia striiformis for wheat ) And other rust diseases, Puccinia hordei against barley, Psnia striiformis and other rust diseases, and other hosts (e.g., turf, rye, coffee, pear, apple, peanut, sugar beet, Rust disease against vegetables and ornamental plants; Erysiphe cichoracearum against pumpkins (eg melon); barley, wheat Powdery mildew (Blumeria graminis) (or Erichife graminis) on rye and turf, and other powdery mildews on various hosts, such as Sphaerotheca macularis for hops, sphaeroseca for pumpkins (e.g. cucumber)・ Sphaerotheca fusca (Sphaerotheca fuliginea), Leveillula taurica for tomatoes, eggplants and peppers, Podosphaera leucotricha for apples, and untuna for wine grapes necator); cereals (eg wheat, barley, rye), turf and other hosts, Cochliobolus species, Helminthosporium species, Drechslera species (Pireno) Pyrenophora), Rhynchosporium, Mycosphaerella graminicola (Septoria tritici) and Phaeosphaeria nodorum (Stagonospora nodolum) Stagonospora nodorum) or Septoria nodorum), Pseudocercosporella herpotrichoides, and Gaeumannomyces graminis; Cercosporidium personatum and other hosts, such as sugar beet, banana, soybean and rice, other Cercospora species; tomatoes, strawberries, vegetables, wine grapes and Botrytis cinerea against other hosts (Botrytis cinerea) and other Botrytis species against other hosts; vegetables (eg carrots), rapeseed, apples, tomatoes, potatoes, grains (eg wheat) and other hosts, Alternaria spp. Including Venturia spp. (Venturia inaequalis) for apples, pears, drupes, tree nuts and other hosts ); Cladosporium species for a wide range of hosts including cereals (eg wheat) and tomatoes; Monilinia species for drupes, nuts and other hosts; tomatoes, turf, wheat, pumpkins And Didymella species for other hosts; Phoma species for rapeseed, turf, rice, potato, wheat and other hosts; Aspergillus for wheat, wood and other hosts Aspergillus and Aureobasidium species; peas, wheat, barley and other hosts, Ascochyta species; apples, pears, onions and other hosts, Stemphylium species (Pleospora species); for apples and pears, summer diseases (eg anthrax (Glomerella cingulata)), black spot or spots Diseases (Botryosphaeria obtusa), apple sunspot (Mycosphaerella pomi), cedar apple rust (Gymnosporangium juniperi-virginianae), soot spot (Gloeodes pomigena) , Soot spot fungus (Schizothyrium pomi) and white rot (Botryosphaeria dothidea)); wine grapes Plasmopara viticola; Bremia lactucae for lettuce, Peronospora species for soybean, tobacco, onion and other hosts, Pseudoperonospora humuli for hops, And other downy mildews such as Pseudoperonospora cubensis for pumpkins; Pythium species (including Pythium ultimum) for turf and other hosts; potatoes and tomatoes Phytophthora infestans against vegetables, strawberries, avocados, peppers, ornamental plants, tobacco, cocoa and other hosts; Phytophthora species; Thanatephorus cucumeris against rice and turf ),common Other Rhizoctonia species for various hosts such as wheat and barley, peanuts, vegetables, cotton and turf; Sclerotinia species for turf, peanut, potato, rapeseed and other hosts; Sclerotium species for turf, peanuts and other hosts; Gibberella fujikuroi for rice; Colletotrichum species for a wide range of hosts including turf, coffee and vegetables; Laetisaria fushiformis for turf (Laetisaria fuciformis); Mycosphaerella species for banana, peanut, citrus, pecan, papaya and other hosts; Diaporthe species for citrus, soybean, melon, pear, lupine and other hosts; Citrus, wine grapes, olives, pecans, roses and other inns Elsinoe spp. Against Vertillium spp. Against a broad range of hosts including hops, potatoes and tomatoes; Pyrenopeziza spp. Against rapeseed and other hosts; cacao basal streak Oncobasidium theobromae causing backs; Fusarium spp., Typhula spp., Microdochium nivale on various hosts, especially on wheat, barley, turf and corn ), Ustilago species, Urocystis species, Tilletia species and Claviceps purpurea; Ramularia species against sugar beet, barley and other hosts Especially post-harvest fungi of fruits (eg Penicillium digita against oranges) Tam (Penicillium digitatum), Penicillium italicum and Trichoderma viride, Colletotrichum musae for bananas and Gloeosporium musarum, and Botrytis bot tis rye for grapes cinerea)); other pathogens for wine grapes, especially Eutypa lata, Guignardia bidwellii, Phellinus igniarus, Phomopsis viticola, Pseudopeza zudo tracheiphila) and Stereum hirsutum; other pathogens against trees (eg Lophodermium seditiosum), or against timber, especially Cephaloscus fragrance ragrans, Ceratocystis spp., Ophiostoma piceae, Penicillium spp., Trichoderma pseudokoningii, Trichoderma viride, Trichoderma viride, Trichoderma viride Aspergillus niger, Leptographium lindbergi and Aureobasidium pullulan; and viral vectors for fungal vectors such as barley yellow mosaic virus (BYMV) Polymyxa graminis and Polymyxa betae against sugar beet as a vector for Rhizomania.

  The compounds of formula (I) may migrate acropetally, basipetally or locally into plant tissue so that they are active against one or more fungi. Furthermore, the compound of formula (I) may be volatilized such that it is sufficient to be active in the vapor phase against one or more fungi on the plant.

  Accordingly, the present invention provides a fungicidal effective amount of a compound of formula (I), or a composition containing a compound of formula (I), to a plant, to a plant seed, to a plant or seed locus. Or a method for controlling or controlling phytopathogenic fungi comprising application to soil or to any other plant growth medium, such as nutrient solution.

As used herein, the term “plant” includes seedlings, shrubs and trees. Furthermore, the fungicidal methods of the present invention include protective treatments, therapeutic treatments, systemic treatments, eradication treatments and anti-spore formation treatments.
The compounds of formula (I) are preferably used in the form of compositions for agricultural, horticultural and turfgrass purposes.

  In order to apply a compound of formula (I) to a plant, plant seed, plant or seed habitat, or soil or to any other growth medium, the compound of formula (I) is usually of formula (I) In addition to a compound of the formula, the composition is formulated into a suitable inert diluent or carrier, and optionally a surfactant (SFA). SFA reduces the interfacial tension, thereby leading to changes in other properties (eg, dispersion, emulsification and wetting), thereby causing the properties of the interface (eg, liquid / solid interface, liquid / gas interface or liquid / liquid interface). Is a chemical that can be changed. All compositions (both solid and liquid formulations) preferably contain 0.0001-95% by weight of the compound of formula (I), more preferably 1-85% by weight, for example 5-60% by weight. The composition is generally used for fungal control, so that the compound of formula (I) is at a rate of 0.1 g to 10 kg / ha, preferably 1 g to 6 kg / ha, more preferably 1 g to 1 kg / ha. Applied.

When used in seed dressing, the compound of formula (I) is from 0.0001 g to 10 g (eg 0.001 g or 0.05 g), preferably from 0.005 g to 10 g, more preferably from 0.001 g / kg seed. Used in a ratio of 005 g to 4 g.
In another aspect, the present invention provides fungicidal compositions containing a fungicidal effective amount of a compound of formula (I) as well as a suitable carrier or diluent for them.

  In a still further aspect, the present invention relates to fungi in a habitat comprising treating the fungus or the fungal habitat with a fungicidally effective amount of a composition comprising a compound of formula (I). A method for removing and controlling This composition comprises powder (DP), aqueous solvent (SP), granular aqueous solvent (SG), granular wettable powder (WG), wettable powder (WP), granule (GR) (sustained release or immediate release) ), Liquid (SL), oil (OL), ultra-low volume liquid (UL), emulsion (EC), concentrated powder (DC), emulsion formulation (both oil-in-water (EW) and water-in-oil (EO)) Choose from many dosage forms, including microemulsion formulation (ME), concentrated suspension (SC), aerosol formulation, fumigation / smoke agent, capsule suspension (CS) and seed treatment formulation it can. The dosage form selected in either case will depend on the particular purpose envisaged and the physical, chemical and biological properties of the compound of formula (I).

  Dust (DP) is a compound of formula (I) that is mixed with one or more solid diluents (eg natural clay, kaolin, calcite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earth, calcium phosphate, calcium carbonate. And magnesium carbonate, sulfur, lime, flour, talc, and other organic and inorganic solid carriers) and mechanically grinding this mixture to a fine powder.

  An aqueous solvent (SP) is used to improve the dispersibility / solubility in water by replacing the compound of formula (I) with one or more water-soluble inorganic salts (eg sodium bicarbonate, sodium carbonate or magnesium sulfate). Or may be prepared by mixing with one or more water-soluble organic solids (eg, polysaccharides), and optionally one or more wetting agents, one or more dispersing agents, or a mixture of these materials. . This mixture is then ground into a fine powder. A similar composition may be granulated to form a granular aqueous solvent (SG).

  A wettable powder (WP) is a compound of formula (I) that promotes dispersion in a liquid, one or more solid diluents or carriers, one or more wetting agents, and preferably one. Or it may be prepared by mixing with a plurality of dispersants and optionally one or more suspending agents. This mixture is then ground into a fine powder. A similar composition may be granulated to form a granular wettable powder (WG).

  Granules (GR) may be obtained by granulating a mixture of a compound of formula (I) and one or more powdered solid diluents or carriers, or a compound of formula (I) (or suitable By absorbing them in a porous granular material (eg pumice, attapulgite clay, fuller's earth, kieselguhr, diatomaceous earth or ground corn cobs) or of formula (I) By adsorbing the compounds (or their solutions in suitable materials) onto a hard core material (eg sand, silicate, inorganic carbonate, sulfate or phosphate) and drying if necessary It may be formed either by granulating from preformed blank granules. Substances commonly used to aid absorption or adsorption include solvents (eg aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and sticking agents (eg polyvinyl acetate, polyvinyl alcohol, dextrin, sugars). Quality and vegetable oil). One or more other additives (eg, emulsifiers, wetting agents or dispersing agents) may also be included in the granules.

  Concentrated powders (DC) may be prepared by dissolving the compound of formula (I) in water or an organic solvent such as a ketone, alcohol or glycol ether. These solutions may contain a surfactant (eg, to improve water dilution or prevent crystallization in a spray tank).

Emulsions (EC) or oil-in-water emulsion formulations (EW) contain a compound of formula (I), an organic solvent (optionally one or more wetting agents, one or more emulsifiers or a mixture of these substances). May be prepared by dissolving in). Suitable organic solvents for use in EC include aromatic hydrocarbons (eg, alkylbenzene or alkylnaphthalene, such as SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a registered trademark), ketones (eg, cyclohexanone or methylcyclohexanone), and alcohols (such as benzyl alcohol, furfuryl alcohol or butanol), N- alkylpyrrolidones (such as N- methylpyrrolidone or N- octylpyrrolidone), dimethyl amides (e.g. C ₈ -C _1O fatty dimethylamide) of fatty acids, and chlorinated There are hydrocarbons. The EC product can spontaneously emulsify upon addition to water to produce an emulsion with sufficient stability to allow application by a suitable device. Preparation of EW can be done as a liquid (if it is not liquid at room temperature, it can melt at a reasonable temperature, typically below 70 ° C.) or in solution (dissolve it in a suitable solvent) To obtain a compound of formula (I), and then emulsify the resulting liquid or solution in water containing one or more SFAs under high shear to produce an emulsion It is necessary to. Suitable solvents for use in EW include vegetable oils, chlorinated hydrocarbons (eg chlorobenzene), aromatic solvents (eg alkylbenzene or alkylnaphthalene) and other suitable organic solvents with low solubility.

  A microemulsion formulation (ME) mixes water with a blend of one or more solvents with one or more SFAs to produce a spontaneously thermodynamically stable isotropic liquid formulation. It may be prepared by making. The compound of formula (I) is initially present in either water or a solvent / SFA blend. Suitable solvents for use in ME include those previously described for use in EC or EW. The ME can be either an oil-in-water or water-in-oil system (which system can be determined by conductivity measurements), and water- and oil-soluble insecticides in the same formulation. May be suitable for mixing. The ME is suitable for dilution in water and either remains as a microemulsion or forms a normal oil-in-water emulsion.

  Concentrated suspensions (SC) may include aqueous and non-aqueous suspensions of finely divided insoluble solid particles of the compound of formula (I). SC is prepared by ball milling or bead milling, in a suitable medium, with a solid compound of formula (I), optionally with one or more dispersants, to make a fine suspension of the compound. You can do it. One or more wetting agents may be included in the composition, and a suspending agent may be included to slow the rate at which the particles settle. Alternatively, the compound of formula (I) may be dry milled and added to water containing the materials previously described to produce the desired end product.

  Aerosol formulations contain a compound of formula (I) and a suitable propellant (eg n-butane). The compound of formula (I) is dissolved or dispersed in a suitable medium (eg water or a water miscible liquid such as n-propanol) to provide a composition for use in a non-pressurized manual spray pump. You can also.

  In order to form a composition suitable for generating smoke containing the compound of formula (I) in an enclosed space, this compound may be mixed dry in a pyrotechnic mixture. .

  Capsule suspension (CS) is similar to the preparation of EW formulations, but in which each oil droplet is encapsulated by a polymeric shell, and the compound of formula (I) and optionally their carrier or diluent May be prepared in a manner that involves an additional polymerization step to obtain an aqueous dispersion of oil droplets. This polymeric shell can be made either by interfacial polycondensation reaction or by a coacervation procedure. These compositions provide controlled release of compounds of formula (I), which may be used for seed treatment. The compound of formula (I) may be formulated in a biodegradable polymer matrix to provide slow controlled release of the compound.

  The composition may be used to improve the biological performance of the composition (eg wettability, retention or distribution on the surface; resistance to rain water on the treated surface; or incorporation of a compound of formula (I) or One or more additives may be included (by improving migration). Such additives include surfactants, oil based spray additives such as certain mineral oils or natural vegetable oils (such as soybean oil and rapeseed oil); and other in vivo enhancements of these substances ( bio-enhancing) adjuvants (components that assist or modify the action of the compound of formula (I)).

  The compound of formula (I) can be used as a seed treatment, for example as a dry seed treatment powder (DS), a water-soluble powder (SS) or a powder composition comprising a water dispersible powder (WS) for slurry treatment or flowable. (FS), solution (LS) or capsule suspension (CS) may be formulated for use as a liquid composition. The preparation of these DS, SS, WS, FS, and LS compositions is very similar to the preparation of the DP, SP, WP, SC, and DC compositions described above, respectively. Compositions for treating seeds may contain substances that aid in the adhesion of the composition to the seed (eg, mineral oil or film-forming barrier). The wetting agent, dispersing agent and emulsifier may be a cationic, anionic, zwitterionic or nonionic SFA.

  Suitable cationic SFAs are quaternary ammonium compounds (eg cetyltrimethylammonium bromide), imidazolines and amine salts. Suitable anionic SFAs include alkali metal salts of fatty acids, salts of aliphatic monoesters of sulfuric acid (eg, sodium lauryl sulfate), salts of sulfonated aromatic compounds (eg, sodium dodecylbenzene sulfonate, dodecylbenzene sulfonic acid) Calcium, butyl naphthalene sulfonate and a mixture of di-isopropyl- and tri-isopropyl-sodium naphthalene sulfonate), sulfuric ether, sulfuric alcohol ether (eg, sodium laureth-3-sulfate), carboxylic acid ether (eg, laureth-3-carboxylic acid) Acid)), phosphate esters (product of reaction between one or more aliphatic alcohols and phosphoric acid (mainly mono-esters) or phosphorus pentoxide (mainly di-esters), eg lauryl alcohol and tetralin Products of the reaction between acids; These products Te may be ethoxylated.), Including sulfosuccinic acid, paraffin or olefin sulfonate, taurates system and lignosulphonates. Suitable zwitterionic SFAs include betaine, propionate and glycinate. Suitable nonionic SFAs are alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, with aliphatic alcohols (eg oleyl alcohol or cetyl alcohol), or alkylphenols (eg octylphenol, nonylphenol or octylcresol). ); Partial esters derived from long chain fatty acids or hexitol anhydride; condensation products of the partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; simple esters (eg Fatty acid polyethylene glycol esters); amine oxides (eg lauryl dimethylamine oxide); and lecithin.

  Suitable suspending agents include hydrocolloids (eg polysaccharides, polyvinyl pyrrolidone or sodium carboxymethylcellulose) and swollen clays (eg bentonite or apatal gite).

  The compound of formula (I) can be applied by any of the known means of applying fungicidal compounds. For example, to any part of the plant, including leaves, stems, branches or roots, or to the seed before planting, or other medium in which the plant is grown or planted (e.g. around the roots) Of soil, soil in general, paddy water or hydroponics system) applied directly or unprepared, or applied by spraying, dressing, dipping, cream or paste As an application, as a steam, or through a spreader, or a composition (eg, a granular composition or a composition filled in a water-soluble bag) may be mixed into the soil or aqueous environment.

  The compounds of formula (I) can also be injected into plants, or sprayed onto vegetation using electrokinetic spray techniques or other low volume methods, or applied by land or local irrigation systems.

  Compositions for use as aqueous preparations (aqueous solutions or dispersions) are generally supplied in the form of concentrates containing a high proportion of active ingredient, which concentrates are added to water before use. These concentrates, which can include DC, SC, EC, EW, ME, SG, SP, WP, WG, and CS, withstand long-term storage and are added to water after such storage and can be It is necessary to be able to form an aqueous preparation that remains homogeneous for a time sufficient to be applied by the device. Such aqueous preparations may contain varying amounts of a compound of formula (I) (eg 0.0001 to 10% by weight) depending on the purpose for which they are used.

The compounds of formula (I) may be used in a mixture with fertilizers (eg nitrogen-, potassium- or phosphorus-containing fertilizers). Suitable dosage forms include fertilizer granules. These mixtures preferably contain up to 25% by weight of the compound of formula (I).
Accordingly, the present invention also provides a fertilizer composition comprising a fertilizer and a compound of formula (I).

  The composition of the present invention may comprise other compounds having biological activity, such as micronutrients, or compounds having similar or supplemental fungicidal activity or plant growth modulating activity, herbicidal activity, insecticidal activity, nematicidal activity or You may contain the compound which has acaricidal activity.

  By containing another fungicide, the resulting composition can have a broader spectrum of activity and a greater level of intrinsic activity than the compound of formula (I) alone. Still other fungicides may have a synergistic effect on the fungicidal activity of the compound of formula (I).

  The compound of formula (I) may be the sole active ingredient of the composition, or it may be one or more of an insecticide, fungicide, synergist, herbicide or plant growth regulator, as appropriate. It may be mixed with a plurality of additional active ingredients. The additional active ingredient provides a composition with a broader spectrum of activity or increased residue at the habitat; synergizes or supplements the activity of the compound of formula (I) (eg, action By increasing speed or overcoming water repellency); or helping to overcome or prevent the emergence of resistance to individual components. The particular additional active ingredient will depend on the intended utility of the composition.

Examples of fungicidal compounds that may be included in the composition of the invention are AC 382042 (N- (1-cyano-1,2-dimethylpropyl) -2- (2,4-dichlorophenoxy) propionamide), Acibenzoral-S-methyl, alanic carb, aldimorph, anilazine, azaconazole, azaphenidine, azoxystrobin, benalaxyl, benomyl, benchavaricarb, biloxazol, viteltanol, blasticidin S, boscalido (new name for nicobifen), bromcon Zazole, bupyrimeto, captahol, captan, carbendazim, carbendazim chlorohydrate, carboxin, carpropamide, carvone, CGA 41396, CGA 41397, quinomethionate, chlorbenzthiazone, chlorothalonil, chlorozolinate, clojiraco For example, copper oxychloride, copper oxyquinolate, copper sulfate, copper oils such as tall oil acid and bordeaux liquid, cyamidazosulfamid, cyazofamide (IKF-916), cyflufenamide, simoxanil, Cybroconazole, Cyprodinil, Debacarb, Di-2-pyridyldisulfide-1,1'-dioxide, Diclofluanide, Diclocimet, Diclomedin, Dichlorane, Dietofencarb, Diphenoconazole, Difenzocote, Diflumetrim, O, O-di-iso-propyl -S-benzylthiophosphoric acid, dimefluazole, dimethconazole, dimethymol, dimethomorph, dimoxystrobin, diniconazole, dinocup, dithianone, dodecyldimethylammonium chloride, dodemorph, dodine, doc Guanidine, edifenphos, epoxiconazole, ethaboxam, ethylimol, ethyl (Z) -N-benzyl-N ([methyl (methyl-thioethylideneaminooxycarbonyl) amino] thio) -β-alaninate, etridiazole, famoxadone, phen Amidone, Phenarimol, Fenbuconazole, Fenfram, Fenhexamide, Phenoxanyl (AC 382042), Fenpiclonyl, Fenpropidin, Fenpropimorph, Triphenyltin acetate, Triphenyltin hydroxide, Farbum, Ferimzone, Fluazinam, Fludioxonil, Flumethover , Flumorph, fluorimide, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriahol, phorpet, Jose Til-aluminum, fuberidazole, flaxil, furametopil, guazatine, hexaconazole, hydroxyisoxazole, himexazole, imazalyl, imibenconazole, iminocazine, iminoctadine triacetate, ipconazole, iprobenphos, iprodione, iprovalicarb, isopropanylbutylcarbamate , Kasugamycin, Cresoxime-methyl, LY186054, LY211795, LY 248908, Mancozeb, Maneb, Mefenoxam, Mepanipyrim, Mepronil, Metalaxyl, Metalaxyl M, Metoconazole, Methylam, Methylam-zinc, Metominostrobin, Metrafenone, MON65500 (N-Allyl) , 5-dimethyl-2-trimethylsilylthiophene-3-carboxamide), microbutanyl, NTN03 01, neoassodin, dimethyl nickel dithiocarbamate, nitrotar-isopropyl, nuarimol, off-race, organomercury compounds, orisatrobin, oxadixyl, oxasulfuron, oxophosphate, oxpoconazole, oxycarboxyl, pefrazoate, penconazole, pencyclon, phenazine oxide , Phosphorus-containing acid, phthalide, picoxystrobin, polyoxin D, polyram, probenazole, prochloraz, prosimidone, propamocarb, propamocarb hydrochloride, propiconazole, propineb, propionic acid, proquinazide, prothioconazole, pyraclostrobin, pyrazophos, Pyriphenox, Pyrimethanyl, Pyroxylone, Piroxyflu, Pyrrolnitrin, Quaternary ammonium compounds, Quinomethio , Quinoxyphene, quintozene, silthiofam (MON 65500), S-imazalyl, cimeconazole, cypconazole, sodium pentachlorophenate, spiroxamine, streptomycin, sulfur, tebuconazole, teclophthalam, technazen, tetraconazole, thiabendazole, tifluzamide, 2- ( Thiocyano-methylthio) benzothiazole, thiophanate-methyl, thiram, thiazinyl, thymibenconazole, tolcrophos-methyl, tolylfluanid, triadimethone, triadimenol, triazbutyl, triazoxide, tricyclazole, tridemorph, trifloxystrobin, triflumizole, Trifolin, Triticonazole, Validamycin A, Vapam, Vinclozoline, XRD-563, Dinebu, Zillam Zoxamide, and a compound of the formula:

  The compounds of formula (I) may be mixed with soil, peat or other rooting media for the protection of plants against seed infectious diseases, soil infectious diseases or leaf fungal diseases.

  Some mixtures can contain active ingredients with significantly different physical, chemical or biological properties, so that they cannot easily be made into the same normal dosage form themselves. In these situations, other dosage forms can be prepared. For example, if one of the active ingredients is a water-insoluble solid and the other is a water-insoluble liquid, nevertheless, the solid active ingredient is dispersed as a suspension (using a preparation similar to the preparation of SC). By dispersing the liquid active ingredient as an emulsion (using a preparation similar to the preparation of EW), it would be possible to disperse each active ingredient in the same continuous aqueous phase. The resulting composition is a suspoemulsion (SE) formulation.

The invention is illustrated by the following examples, in which the following abbreviations are used:
ml = milliliter m. p. = Melting point (no correction)
g = gram b. p. = Boiling point THF = tetrahydrofuran DMSO = dimethylsulfoxide M ⁺ = mass ion DMF = N, N-dimethylformamide s = singlet d = doublet HOBT = 1-hydroxybenzotriazole HOAT = 7-aza-1-hydroxybenzotriazole bs = Broad singlet NMR = nuclear magnetic resonance t = triplet HPLC = high performance liquid chromatography q = quartet TLC = thin layer chromatography m = multiplet glc = gas-liquid chromatography ppm = parts per million EDC = 1 -Ethyl-3-N, N-dimethylaminopropylcarbodiimide hydrochloride M = mol

Example 1
This example illustrates the preparation of 2- (3-bromo-7-chloro-quinolin-6-yloxy) -N-tert-butyl-2-methylsulfanyl-acetamide (Compound 12 of Table 2).
Stage 1 : Preparation of 3-bromo-7-chloro-quinolin-6-ol
Process 1
3-Chloro-4-methoxyaniline (10 g) in acetic acid (100 ml) was treated with 2,2,3-tribromopropanal (18.8 g) and the mixture was stirred at room temperature for 2 hours, This was then diluted with water and extracted with ethyl acetate. The organic phase is washed with 2N NaOH, dried over sodium sulfate, filtered, evaporated under reduced pressure and after chromatography (silica; hexane / ethyl acetate) the desired product 3-bromo-7-chloro- 6-Methoxy-quinoline was obtained as a yellow solid (M ⁺ 274). ¹ H NMR (CDCl ₃ ) δ ppm: 8.78 (1H, d); 8.21 (1H, d); 8.10 (1H, s); 7.03 (1H, s).

Process 2
A mixture (100 ml × 2) of the product of Step 1 (1.4 g) and hydrobromic acid (48% by weight solution in water) was refluxed for 62 hours. The mixture was cooled to ambient temperature, diluted with water, treated with sodium bicarbonate and extracted with ethyl acetate. The extract was dried over magnesium sulfate, filtered and evaporated under reduced pressure to give the required product 3-bromo-7-chloro-quinolin-6-ol (M ⁺ 260). ¹ H NMR (DMSO) δ ppm: 7.34 (1H, s); 7.07 (1H, s); 8.60 (1H, d); 8.73 (1H, d); 11.12 (1H, s).

Stage 2 : Preparation of (3-bromo-7-chloro-quinolin-6-yloxy) -methylsulfanyl-acetic acid methyl ester
Process 1
Sulfuryl chloride (8.1 ml) was added dropwise to a stirred solution of methyl (methylthio) acetate (10.8 ml) in dichloromethane (300 ml) cooled to −15 ° C. The mixture was warmed to room temperature over 2 hours and then concentrated under reduced pressure to give crude chloro-methylsulfanyl-acetic acid methyl ester as a colorless liquid. This product was used in the next step without further purification. ¹ H NMR (CDCl ₃ ) δ ppm: 2.33 (3H, s); 3.83 (3H, s); 5.49 (1H, s).

Process 2
To a stirred solution of stage 1 step 2 3-bromo-7-chloro-quinolin-6-ol (1.1 g) at ambient temperature in anhydrous DMF (17 ml) containing anhydrous potassium carbonate (3.1 g). Chloro-methylsulfanyl-acetic acid methyl ester (0.79 g) was added dropwise. The mixture was heated at 60-65 ° C. for 1 hour, cooled to ambient temperature, diluted with water and extracted with ethyl acetate. The extracts were combined, washed with brine, dried over magnesium sulfate, filtered and evaporated under reduced pressure. Purification of the crude material by chromatography (silica; ethyl acetate / hexane volume ratio 1: 4) yielded the title compound (3-bromo-7-chloro-quinolin-6-yloxy) -methylsulfanyl-acetic acid methyl ester ( M ⁺ 378). ¹ H NMR (CDCl ₃ ) δ ppm: 2.29 (3H, s); 3.89 (3H, s); 5.74 (1H, s) 7.18 (1H, 8); 8.16 (1H, s); 8.23 (1H, s) ; 8.82 (1H, s).

Stage 3 : Preparation of (3-Bromo-7-chloro-quinolin-6-yloxy) -methylsulfanyl-acetic acid To a stirred solution (1.1 g) of the product of Stage 2 Step 2 in ethanol (14 ml) at ambient temperature 2N sodium hydroxide solution (2.2 ml) with water as solvent was added. The mixture was stirred at room temperature for 1 hour, then poured into ice-water and acidified with 2M hydrochloric acid. The resulting precipitate was filtered from solution, washed with cold water, and dried in vacuo, (3-bromo-7-chloro - 6-yloxy) - methylsulfanyl - to give acetic acid (M ⁺ 364). ¹ H NMR (DMSO-d6) δ ppm: 2.20 (3H, s); 6.18 (1H, s) 7.57 (1H, s); 8.19 (1H, s); 8.28 (1H, d); 8.88 (1H, d ); 13.7 (1H, bs).

Stage 4 : Preparation of 2- (3-Bromo-7-chloro-quinolin-6-yloxy) -N-tert-butyl-2-methylsulfanyl-acetamide Said stage 3 in anhydrous N, N-dimethylformamide (2 ml) The product of (3-bromo-7-chloro-quinolin-6-yloxy) -methylsulfanyl-acetic acid (85 mg), t-butylamine (17 mg), N- (3-dimethylamino-propyl) -N′-ethyl Treated with carbodiimide hydrochloride (45 mg), HOAt (32 mg) and triethylamine (24 mg) at ambient temperature with stirring for 3 hours. The mixture is poured into water and extracted with ethyl acetate (3 times), the extracts are combined, washed with saturated aqueous sodium carbonate, water (3 times), then dried over magnesium sulfate and filtered. And evaporated under reduced pressure to give an oil. This oil was fractionated by chromatography (silica; hexane / ethyl acetate volume ratio 3: 1) to yield the required product as a white solid (mp 172 ° -174 ° C., M ⁺ 419). ¹ H NMR (CDCl ₃ ) δ ppm: 1.46 (9H, s); 2.18 (3H, s); 5.63 (1H, s); 6.89 (1H, bs); 7.28 (1H, s); 7.28 (1H, s ); 8.18 (1H, s), 8.27 (1H, d); 8.83 (1H, d).

The following amide was prepared using a similar procedure.
Compound 238 of Table 2 using 1,1-dimethyl-prop-2-ynylamine, m. p. 169-171 ° C .; ¹ H NMR (CDCl ₃ ) δ ppm: 1.75 (6H, s); 2.19 (3H, s); 2.41 (1H, s); 5.69 (1H, s); 7.16 (1H, bs); 7.29 (1H, s); 8.18 (1H, s); 8.27 (1H, d); 8.83 (1H, d).

Compound 52 in Table 2: using 2-amino-3-methoxy-2-methyl-propionitrile, ¹ H NMR (CDCl ₃ ) δ ppm: diastereomeric mixture (1/1); 1.82 and 1.84 (3H, 2.18 and 2.20 (3H, 2xs); 3.52 and 3.53 (3H, 2xs); 3.64-3.84 (2H, 2xdd); 5.76 and 5.77 (1H, 2xs); 7.29 and 7.30 (1H, 2xs); 7.59 and 7.61 (1H, 2xbs); 8.18 (1H, s); 8.29 (1H, d); 8.85 (1H, s).

Compound 244 in Table 2: using 1,1-dimethyl-but-2-ynylamine, m. p. 160-162 ° C; ¹ H NMR (CDCl ₃ ) δ ppm: 1.71 (6H, s); 1.83 (3H, s); 2.19 (3H, s); 5.66 (1H, s); 7.15 (1H, bs); 7.27 (1H, s); 8.18 (1H, s); 8.27 (1H, d); 8.83 (1H, d).

Compound 251 of Table 2 using 4-methoxy-1,1-dimethyl-but-2-ynylamine, m.p. p. 124-125 ° C .; ¹ H NMR (CDCl ₃ ) δ ppm: 1.75 (6H, s); 2.19 (3H, s); 3.39 (3H, s); 4.13 (2H, s); 5.67 (1H, s); 7.17 (1H, bs); 7.28 (1H, s); 8.18 (1H, s); 8.28 (1H, d); 8.84 (1H, d).

Example 2
This example illustrates the preparation of 2- (3-bromo-7-methyl-quinolin-6-yloxy) -N-tert-butyl-2-methylsulfanyl-acetamide (Compound 12 of Table 13).
Stage 1 : Preparation of 3-bromo-7-methyl-quinolin-6-ol 4-Amino-2-methyl-phenol (5 g) in acetic acid (60 ml) was added to 2,2,3-tribromopropanal (11 9 g) and the mixture was stirred at room temperature for 3 hours, after which it was diluted with water and extracted with ethyl acetate. The organic phase is washed with aqueous NH ₄ OH, dried over sodium sulfate, filtered and evaporated under reduced pressure to give the required product 3-bromo-7-methyl-6-quinolin-6-ol, This was used as such in the next step (M ⁺ 240). ¹ H NMR (DMSO-d6) δ ppm: 2.32 (3H, s); 7.12 (1H, s); 7.75 (1H, s); 8.46 (1H, d); 8.64 (1H, d); 10.35 (1H, bs).

Stage 2 : Preparation of methyl 3-bromo-7-methyl-quinolinyl-6-oxy-2-methylthioacetate In the same procedure as stage 2 step 2 of Example 1, 3-bromo-7-methyl-quinoline-6- All was treated with methyl 2-bromo-2-methylthioacetate to give methyl 3-bromo-7-methyl-quinolinyl-6-oxy-2-methylthio-acetate (M ⁺ 358). ¹ H NMR (CDCl ₃ ) δ ppm: 2.25 (3H, s); 2.50 (3H, s); 3.88 (3H, s); 5.73 (1H, s); 6.99 (1H, s); 7.86 (1H, s ); 8.19 (1H, d), 8.76 (1H, d).

Stage 3 : Preparation of (3-Bromo-7-methyl-quinolin-6-yloxy) -methylsulfanyl-acetic acid In a similar procedure as in Stage 3 of Example 1, 3-bromo-7-methyl-quinolinyl-6-oxy 2-Methylthio-methyl acetate was hydrolyzed to give (3-bromo-7-methyl-quinolin-6-yloxy) -methylsulfanyl-acetic acid (M ⁺ 344). ¹ H NMR (DMSO) δ ppm: 2.19 (3H, s); 2.42 (3H, s); 6.07 (1H, s); 7.42 (1H, s); 7.86 (1H, s); 8.52 (1H, s) , 8.78 (1H, s), 13.55 (1H, bs).

Stage 4 : Preparation of 2- (3-Bromo-7-methyl-quinolin-6-yloxy) -N-tert-butyl-2-methylsulfanyl-acetamide In the same procedure as in Stage 4 of Example 1, 3-Bromo-7-methyl-quinolinyl-6-oxy) -2-methylthioacetic acid is condensed with t-butylamine to give 2- (3-bromo-7-methyl-quinolin-6-yloxy) -N-tert- Butyl-2-methylsulfanyl-acetamide was obtained (mp 132-134 ° C., M ⁺ 344). ¹ H NMR (CDCl ₃ ) δ ppm: 1.44 (9H, s); 2.19 (3H, s); 2.49 (3H, s); 5.60 (1H, s); 6.48 (1H, bs); 7.10 (1H, s ); 7.89 (1H, s); 8.21 (1H, d); 8.78 (1H, d).

The following amides were prepared using a similar procedure.
Compound 16 in Table 13: 1,1-dimethyl-propylamine used, m. p. 135-137 ° C; ¹ H NMR (CDCl ₃ ) δ ppm: 0.88 (3H, t); 1.39 (6H, s); 1.79 (2H, q); 2.20 (3H, s); 2.48 (3H, s); 5.59 (1H, s); 6.39 (1H, bs); 7.10 (1H, s); 7.89 (1H, s); 8.21 (1H, d); 8.78 (1H, d).

Compound 238 in Table 13: using 1,1-dimethyl-prop-2-ynylamine, m.p. p. 141-146 ° C; ¹ H NMR (CDCl ₃ ) δ ppm: 1.74 (6H, s); 2.19 (3H, s); 2.41 (1H, s); 2.50 (3H, s); 5.65 (1H, s); 6.77 (1H, bs); 7.10 (1H, s); 7.89 (1H, s); 8.21 (1H, d); 8.78 (1H, d).

Compound 52 in Table 13: using 2-amino-3-methoxy-2-methyl-propionitrile; ¹ H NMR (CDCl ₃ ) δ ppm: diastereomeric mixture (1/1); 1.81 and 1.83 (3H, 2xs); 2.20 and 2.21 (3H, 2xs); 2.48 (3H, s); 3.50 and 3.53 (3H, 2xs); 3.61-3.82 (2H, 2xdd); 5.72 and 5.75 (1H, 2xs); 7.11 and 7.13 ( 1H, 2xs); 7.32 and 7.34 (1H, 2xbs); 7.90 (1H, s); 8.23 (1H, s); 8.79 (1H, s).

Compound 221 in Table 13: Use of 1,1-dimethyl-2-prop-2-ynyloxy-ethylamine, m.p. p. 114-116 ° C .; ¹ H NMR (CDCl ₃ ) δ ppm: 1.41 (3H, s); 1.44 (3H, s); 2.18 (3H, s); 2.50 (1H, t); 3.54 (2H, dd); 4.19 (2H, d); 5.61 (1H, s); 6.92 (1H, bs); 7.10 (1H, s); 7.88 (1H, s); 8.22 (1H, d); 8.77 (1H, d).

Compound 251 in Table 13: Use of 4-methoxy-1,1-dimethyl-but-2-ynylamine, m.p. p. 129-132 ° C .; ¹ H NMR (CDCl ₃ ) δ ppm: 1.73 (6H, s); 2.20 (3H, s); 2.49 (3H, s); 3.37 (3H, s); 4.11 (2H, s); 5.63 (1H, s); 6.76 (1H, bs); 7.10 (1H, s); 7.89 (1H, s); 8.21 (1H, d); 8.78 (1H, d).

Example 3
This example illustrates the preparation of 2- (3-bromo-7-fluoro-quinolin-6-yloxy) -N-tert-butyl-2-methylsulfanyl-acetamide (Compound 12 of Table 6).
Stage 1 : Preparation of 3-bromo-7-fluoro-quinolin-6-ol
Process 1
In a manner similar to Stage 1, Step 1 of Example 1, 3-fluoro-4-methoxy-phenylamine (2 g) in acetic acid (25 ml) was converted to 2,2,3-tribromopropanal (4.2 g). To give 3-bromo-7-fluoro-6-methoxy-quinoline (M ⁺ 258). ¹ H NMR (CDCl ₃ ) δ ppm: 4.02 (3H, s); 7.07 (1H, d); 7.75 (1H, d); 8.23 (1H, d); 8.78 (1H, d).

Process 2
In the same procedure as Stage 1 Step 1 of Example 1, 3-bromo-7-fluoro-6-methoxy-quinoline obtained from the previous step was treated with hydrobromic acid to give 3-bromo-7-fluoro. -Quinolin-6-ol was obtained (M ⁺ 244). ¹ H NMR (DMSO-d6) δ ppm: 7.35 (1H, d); 7.77 (1H, d); 8.59 (1H, d); 8.74 (1H, d), 10.93 (1H, s).

Stage 2 : Preparation of (3-bromo-7-fluoro-quinolin-6-yloxy) -methylsulfanyl-acetic acid methyl ester 3-Bromo obtained from the previous step in the same procedure as Stage 2 Step 2 of Example -7-Fluoro-quinolin-6-ol is reacted with methyl 2-bromo-2-methylthioacetate obtained from stage 2 step 1 of Example 1 to give 3-bromo-7-fluoro-quinolinyl-6-oxy- Methyl 2-methylthioacetate was obtained (M ⁺ 362). ¹ H NMR (CDCl ₃ ) δ ppm: 2.27 (3H, s); 3.89 (3H, s); 5.77 (1H, s) 7.26 (1H, d); 7.77 (1H, s); 8.23 (1H ₁ s) ; 8.83 (1H, s).

Stage 3 : Preparation of (3-Bromo-7-fluoro-quinolin-6-yloxy) -methylsulfanyl-acetic acid 2-Methylthio-methyl acetate was hydrolyzed to give (3-bromo-7-fluoro-quinolin-6-yloxy) -methylsulfanyl-acetic acid (M ⁺ 348). ¹ H NMR (DMSO-d6) δ ppm: 6.16 (1H, s); 7.71 (1H, d) 7.90 (1H, d); 8.62 (1H, d), 8.88 (1H, d), 13.69 (1H, bs ).

Stage 4 : Preparation of 2- (3-Bromo-7-fluoro-quinolin-6-yloxy) -N-tert-butyl-2-methylsulfanyl-acetamide In a procedure similar to Stage 4 of Example 1, 3-Bromo-7-fluoro-quinolinyl-6-oxy) -2-methylthioacetic acid is condensed with t-butylamine to give 2- (3-bromo-7-fluoro-quinolin-6-yloxy) -N-tert- Butyl-2-methylsulfanyl-acetamide was obtained (mp 144-145 ° C., M ⁺ 403). ¹ H NMR (CDCl ₃ ) δ ppm: 1.45 (9H, s); 2.19 (3H, s); 5.62 (1H, s); 6.62 (1H, bs); 7.30 (1H, d); 7.79 (1H, d ); 8.26 (1H ₁ d), 8.84 (1H, d).

The following amide was prepared using a similar procedure.
Compound 238 in Table 6: using 1,1-dimethyl-prop-2-ynylamine, m.p. p. 167-169 ° C; ¹ H NMR (CDCl ₃ ) δ ppm: 1.75 (6H, s); 2.21 (3H, s); 2.41 (1H, s); 2.50 (3H, s); 5.68 (1H, s); 6.89 (1H, bs); 7.33 (1H, d); 7.79 (1H, d); 8.26 (1H, d); 8.84 (1H, d).

Compound 52 in Table 6: using 2-amino-3-methoxy-2-methyl-propionitrile, ¹ H NMR (CDCl ₃ ) δ ppm: diastereomeric mixture (1/1); 1.81 and 1.83 (3H, 2.21 and 2.22 (3H, 2xs); 3.52 and 3.54 (3H, 2xs); 3.64-3.84 (2H, 2xdd); 5.75 and 5.76 (1H, 2xs); 7.33-7.36 (2H, m); 7.80 ( 1H, d); 8.28 (1H, d); 8.85 (1H, d).

Compound 221 of Table 6, using 1,1-dimethyl-2-prop-2-ynyloxy-ethylamine, m.p. p. 115-117 ° C; ¹ H NMR (CDCl ₃ ) δ ppm: 1.44 (3H, s); 1.46 (3H, s); 2.20 (3H, s); 2.45 (1H, t); 3.61 (2H, dd); 4.20 (2H, d); 5.63 (1H, s); 6.90 (1H, bs); 7.28 (1H, d); 7.78 (1H, d); 8.26 (1H, d); 8.83 (1H, d).

Compound 251 in Table 6: using 4-methoxy-1,1-dimethyl-but-2-ynylamine, m.p. p. 115-117 ° C; ¹ H NMR (CDCl ₃ ) δ ppm: 1.74 (6H, s); 2.21 (3H, s); 2.49 (3H, s); 3.38 (3H, s); 4.12 (2H, s); 5.65 (1H, s); 6.88 (1H, bs); 7.31 (1H, d); 7.79 (1H, d); 8.26 (1H, d); 8.84 (1H, d).

Compound 244 in Table 6: using 1,1-dimethyl-but-2-ynylamine, m. p. 130-132 ° C; ¹ H NMR (CDCl ₃ ) δ ppm: 1.70 (6H, s); 1.83 (3H, s); 2.21 (3H, s); 5.65 (1H, s); 6.86 (1H, bs); 7.31 (1H, d); 7.78 (1H, d); 8.25 (1H, d); 8.84 (1H, d).

Compound 68 in Table 6: using 2-ethoxy-1,1-dimethyl-ethylamine, m.p. p. 111-113 ° C; ¹ H NMR (CDCl ₃ ) δ ppm: 1.21 (3H, t); 1.43 (H, s); 1.46 (3H, s); 2.20 (3H, s); 3.43 (2H, dd); 3.51-3.58 (2H, m), 5.63 (1H, s); 7.17 (1H, bs); 7.28 (1H, d); 7.78 (1H, d); 8.25 (1H, d); 8.83 (1H, d) .

Compound 277 in Table 6: using 5-methoxy-1,1-dimethyl-pent-2-ynylamine, m.p. p. 104-106 ° C; ¹ H NMR (CDCl ₃ ) δ ppm: 1.71 (6H, s); 2.20 (3H, s); 2.48 (2H, t); 3.37 (3H, s); 3.50 (2H, t); 5.65 (1H, s); 6.88 (1H, bs); 7.31 (1H, d); 7.79 (1H, d); 8.26 (1H, d); 8.84 (1H, d).

Compound 256 in Table 6: using 6-chloro-1,1-dimethyl-hex-2-ynylamine, m.p. p. 95-97 ° C; ¹ H NMR (CDCl ₃ ) δ ppm: 1.70 (6H, s); 1.96 (2H, quin), 2.20 (3H, s); 2.90 (2H, t); 3.68 (2H, t); 3.50 (2H, t); 5.66 (1H, s); 6.87 (1H, bs); 7.31 (1H, d); 7.79 (1H, d); 8.26 (1H, d); 8.84 (1H, d).

Example 4
This example illustrates the preparation of 2- (3-iodo-7-fluoro-quinolin-6-yloxy) -N-tert-butyl-2-methylsulfanyl-acetamide (Compound 12 of Table 7).
Stage 1 : Preparation of 3-iodo-6-hydroxyquinoline Example 3 Stage 1 Step 2 3-bromo-7-fluoro-6-hydroxyquinoline (0.50 g) in dioxane (3.0 ml), sodium iodide Add N, N, N ′, N′-tetramethyl-ethane-1,2-diamine (0.07 g) in a sealed tube to a stirred mixture of (0.62 g) and copper iodide (0.08 g) did. The mixture was stirred at 120 ° C. for 14 hours and, upon cooling, treated with an aqueous ammonia solution followed by an aqueous hydrochloric acid solution. Extraction with ethyl acetate, drying of the organic phase over magnesium sulfate, filtration and evaporation under reduced pressure yields the required product (M ⁺ 290) as a light brown colored powder which is used directly in the next step. did. ¹ H NMR (CDCl ₃ ) δ ppm: 7.30 (1H, d); 7.72 (1H, d); 8.02 (1H, d), 8.73 (1H, d); 8.83 (1H, d), 10.88 (1H, s ).

Stage 2 : Preparation of N-tert-butyl-2- (3-iodo-7-fluoro-quinolin-6-yloxy) -2-methylsulfanyl-acetamide In the same procedure as Stage 1 Step 1 of Example 1, -Iodo-7-fluoro-6-hydroxy-quinoline was reacted with chloromethylsulfanyl-acetic acid ethyl ester to give (3-iodo-7-fluoro-quinolin-6-yloxy) -methylsulfanyl-acetic acid ethyl ester (M ⁺ 408). (3-Iodo-7-fluoro-quinolin-6-yloxy) -methylsulfanyl-acetic acid ethyl ester was hydrolyzed in the same procedure as in stage 3 of Example 1, and (3-iodo-7-fluoro-quinoline- 6-yloxy) -methylsulfanyl-acetic acid (M ⁺ 394) was obtained. In a similar procedure as in Stage 4 of Example 1, (3-iodo-7-fluoro-quinolin-6-yloxy) -methylsulfanyl-acetic acid is condensed with t-butylamine to give N-tert-butyl-2- ( 3-Iodo-quinolin-6-yloxy) -2-methylsulfanyl-acetamide was obtained as a white solid (mp 165-166 ° C., M ⁺ 449). ¹ H NMR (CDCl ₃ ) δ ppm: 1.44 (9H, s); 2.18 (3H, s); 5.60 (1H, s); 6.62 (1H, bs); 7.27 (1H, d); 7.76 (1H, dd ); 8.47 (1H, d); 8.97 (1H, d).

The following amide was prepared using a similar procedure.
Compound 238 in Table 7: using 1,1-dimethyl-prop-2-ynylamine, m.p. p. 150-152 ° C; ¹ H NMR (CDCl ₃ ) δ ppm: 1.75 (6H, s); 2.20 (3H, s); 2.40 (1H, s); 5.66 (1H, s); 6.88 (1H, bs); 7.27 (1H, s); 7.77 (1H, s); 8.47 (1H, d); 8.97 (1H, d).

Compound 52 in Table 7: using 2-amino-3-methoxy-2-methyl-propionitrile, ¹ H NMR (CDCl ₃ ) δ ppm: diastereomeric mixture (1/1); 1.82 and 1.84 (3H, 2xs); 2.20 and 2.22 (3H, 2xs); 3.53 and 3.54 (3H, 2xs); 3.64-3.84 (2H, 2xdd); 5.73 and 5.75 (1H, 2xs); 7.27-7.36 (3H, m); 7.77 ( 1H, d); 8.49 (1H, d); 8.98 (1H, s).

Compound 244 in Table 7: using 1,1-dimethyl-but-2-ynylamine, m. p. 142-145 ° C; ¹ H NMR (CDCl ₃ ) δ ppm: 1.70 (6H, s); 1.83 (3H, s); 2.20 (3H, s); 5.64 (1H, s); 6.87 (1H, bs ); 7.27 (1H, d); 7.76 (1H, d); 8.47 (1H, d); 8.96 (1H, d).

Compound 251 in Table 7: using 4-methoxy-1,1-dimethyl-but-2-ynylamine, m.p. p. 110-112 ° C; ¹ H NMR (CDCl ₃ ) δ ppm: 1.74 (6H, s); 2.20 (3H, s); 3.38 (3H, s); 4.13 (2H, s); 5.65 (1H, s); 6.89 (1H, bs); 7.27 (1H, d); 7.78 (1H, d); 8.47 (1H, d); 8.97 (1H, d).

Example 5
This example illustrates the preparation of N-tert-butyl-2- (7-fluoro-3-thiophen-3-yl-quinolin-6-yloxy) -2-methylsulfanyl-acetamide (Compound 12 of Table 30). is doing.
Stage 1 : Example 3 Stage 4 2- (3-Bromo-7-fluoro-quinolin-6-yloxy) -N-tert-butyl-2 in dioxane / water (1: 1 mixture, 4.8 ml) A stirred mixture of methylsulfanyl-acetamide (160 mg), bis (triphenylphosphine) palladium (II) chloride (1.4 mg), 3-thiopheneboronic acid (56 mg) and sodium bicarbonate (101 mg) at 70 ° C. Heated for 14 hours. Upon cooling, the reaction mixture was treated with saturated aqueous sodium bicarbonate (5 ml). Extraction with ethyl acetate, drying of the organic phase over magnesium sulfate, filtration and evaporation under reduced pressure gives a crude product which is fractionated by chromatography (silica; hexane / ethyl acetate volume ratio 2: 1). The required product was obtained as a white solid (mp 170-173 ° C., M ⁺ 405). ¹ H NMR (CDCl ₃ ) δ ppm: 1.46 (9H, s); 2.20 (3H, s); 5.64 (1H, s); 6.66 (1H, bs); 7.42 (1H, d); 7.51 (2H, m ); 7.66 (1H, m), 7.80 (1H, d), 8.22 (1H, d); 9.13 (1H, d).

The following amide was prepared by a similar procedure. 2- (7-Fluoro-3-thiophen-3-yl-quinolin-6-yloxy) -N- (4-methoxy-1,1-dimethyl-but-2-ynyl) -2-methyl-sulfanyl-acetamide ( Compound 251) in Table 30) m. p. 132-134 ° C .; ¹ H NMR (CDCl ₃ ) δ ppm: 1.75 (6H, s); 2.22 (3H, s); 3.39 (3H, s); 4.13 (2H, s); 5.68 (1H, s); 6.93 (1H, bs); 7.42 (1H, d); 7.51 (2H, m); 7.66 (1H, m), 7.82 (1H, d), 8.22 (1H, d); 9.13 (1H, d) Example 3 Stage 4, 2- (3-Bromo-7-fluoro-quinolin-6-yloxy) -N- (4-methoxy-1,1-dimethyl-but-2-ynyl) -2-methylsulfanyl- Prepared from acetamide.

Example 6
This example illustrates the fungicidal properties of the compounds of formula (I). These compounds were tested in the leaf disc assay by the method detailed below. Test compounds were dissolved in DMSO and diluted to 200 ppm with water. For the phytium ultimum test, they were dissolved in DMSO and diluted to 20 ppm with water.

  Erysiphe graminis f. Sp. Tritici (wheat powdery mildew): Wheat leaf fragments were placed on agar in a 24-well plate and sprayed with a solution of the test compound. After complete drying for 12-24 hours, the leaf discs were inoculated with a fungal spore suspension. Following appropriate incubation, the activity of the compounds was evaluated as protective fungicidal activity on day 4 after inoculation.

  Puccinia recondita f. Sp. Tritici (wheat red rust): Wheat leaf fragments were placed on agar in a 24-well plate and sprayed with a solution of the test compound. After complete drying for 12-24 hours, the leaf discs were inoculated with a fungal spore suspension. After appropriate incubation, the activity of the compounds was evaluated as protective fungicidal activity 9 days after inoculation.

  Septoria Nodolm (Wheat Blight): Wheat leaf pieces were placed on agar in a 24-well plate and sprayed with a solution of the test compound. After complete drying for 12-24 hours, the leaf discs were inoculated with a fungal spore suspension. Following appropriate incubation, the activity of the compounds was evaluated as protective fungicidal activity on day 4 after inoculation.

  Pirenophora tres (barley net blotch): Barley leaf fragments were placed on agar in a 24-well plate and sprayed with a solution of the test compound. After complete drying for 12-24 hours, the leaf discs were inoculated with a fungal spore suspension. Following appropriate incubation, the activity of the compounds was evaluated as protective fungicidal activity on day 4 after inoculation.

  Pyricularia oryzae (rice blast disease): Rice leaf fragments were placed on agar in a 24-well plate and sprayed with a solution of the test compound. After complete drying for 12-24 hours, the leaf discs were inoculated with a fungal spore suspension. Following appropriate incubation, the activity of the compounds was evaluated as protective fungicidal activity on day 4 after inoculation.

  Botrytis cinerea (gray mold disease): Bean leaf discs were placed on agar in a 24-well plate and sprayed with a solution of the test compound. After complete drying for 12-24 hours, the leaf discs were inoculated with a fungal spore suspension. Following appropriate incubation, the activity of the compounds was evaluated as protective fungicidal activity on day 4 after inoculation.

  Phytophthora infestance (tomato grafted potato plague): Tomato leaf discs were placed on water agar in a 24-well plate and sprayed with a solution of the test compound. After complete drying for 12-24 hours, the leaf discs were inoculated with a fungal spore suspension. Following appropriate incubation, the activity of the compounds was evaluated as protective fungicidal activity on day 4 after inoculation.

  Plasmopara vitikola (mildew of wine grapes): Wine grape leaf discs were placed on agar in a 24-well plate and sprayed with a solution of the test compound. After complete drying for 12-24 hours, the leaf discs were inoculated with a fungal spore suspension. Following appropriate incubation, the activity of the compounds was evaluated as protective fungicidal activity on day 7 after inoculation.

  Septoria Tortiti (leaf blight): Frozen-stored fungal conidia were mixed directly into a nutrient broth (PDB potato dextrose broth). A (DMSO) solution of the test compound was placed in a microtiter plate (96-well format) and then a nutrient broth containing fungal spores was added. These test plates were incubated at 24 ° C. and after 72 hours growth inhibition was determined photometrically.

  Fusarium carmolum (root rot): Frozen-stored fungal conidia were mixed directly into a nutrient broth (PDB potato dextrose broth). A (DMSO) solution of the test compound was placed in a microtiter plate (96-well format) and then a nutrient broth containing fungal spores was added. These test plates were incubated at 24 ° C. and after 48 hours growth inhibition was determined photometrically.

  Phytium Ultimum (withering disease): Fungal mycelium fragments prepared from fresh liquid cultures were mixed with potato dextrose broth. A solution of the test compound in dimethyl sulfoxide was diluted to 20 ppm with water and then placed in a 96-well microtiter plate and a nutrient broth containing fungal spores was added. The test plates were incubated at 24 ° C. and after 48 hours growth inhibition was determined photometrically.

  The following compounds (first compound number followed by table number in parenthesis) resulted in at least 60% control of the following fungal infection at 200 ppm: Plasmopara viticola, Compound 9 (6) , 12 (7), 38 (6), 52 (6), 52 (7), 60 (6), 95 (6), 221 (6), 221 (13), 235 (6), 238 (7) , 238 (10), 244 (6), 244 (7), 251 (2), 251 (7), 251 (10), 251 (13), 251 (30), 256 (6), 264 (6) , 277 (6), 278 (6), Phytophthora infestans, compounds 12 (6), 12 (10), 52 (7), 52 (13), 221 (6), 221 (13) , 238 (7), 238 (10), 238 (13), 244 (6), 244 (7), 251 (7), 251 (10), 256 (6), 275 (7), 277 (6) 278 (6), Erysiphe graminis f.sp.tritici, compounds 9 (6), 12 (6), 12 (13), 28 (6), 38 (6), 52 (6), 52 (7), 52 (13), 68 (6), 86 (6), 181 (6), 189 (6), 221 (6), 221 (13), 235 (6), 238 (6), 238 (7), 238 (10), 238 (13), 244 (6), 251 (6), 251 (7), 251 (13), 251 (30), 256 (6) , 264 (6), 268 (6), 275 (6), 275 (7), 277 (6), 278 (6), 281 (6), 284 (6), Pyricularia oryzae, compound 9 (6), 52 (6), 52 (7), 68 (6), 221 (6), 238 (6), 244 (7), 251 (6), 251 (7), 275 (7), 277 (6), 278 (6), wheat rust fungus (Puccinia recondita f. Sp. Tritici), compounds 52 (6), 52 (7), 68 (6), 221 (6), 238 (7), 251 (2), 264 (6), Septoria nodorum, Compound 9 (6), 12 (2), 12 (7), 12 (10), 12 (13), 12 (30), 52 ( 6), 52 (7), 68 (6), 221 (6), 235 (6), 238 (6), 238 (7), 244 (6), 244 (7), 244 (13), 251 ( 6), 251 (7), 251 (13), 256 (6), 264 (6), 277 (6), 278 (6), 281 (6), Septoria tritici, compound 9 (6 ), 12 (6), 12 (7), 12 (13), 16 (13), 38 (6), 52 (2), 52 (6), 52 (7), 52 (13), 68 (6 ), 95 (6), 122 (6), 221 (6), 221 (13), 224 (6), 235 (6), 238 (6), 238 (7), 238 (13), 244 (2 ), 244 (6), 244 (7), 251 (6), 251 (7), 251 (13), 251 (2), 251 (30), 256 (6), 264 (6), 268 (6 ), 275 (7), 277 (6), 278 ( 6), 281 (6), 284 (6), 287 (6), 291 (6), Fusarium culmorum, Compound 9 (6), 12 (6), 12 (7), 221 (6 ), 238 (6), 238 (7), 244 (6), 244 (7), 251 (6), 251 (7), 251 (13), 284 (6). The following compounds first compound number, followed by table number in parenthesis) resulted in at least 60% control of the following fungal infections at 20 ppm: Pythium ultimum, compound 9 (6) , 12 (10), 52 (6), 52 (13), 221 (6), 221 (13), 235 (6), 238 (6), 244 (6), 251 (6), 251 (10) 251 (13), 251 (30), 264 (6), 275 (7), 278 (6), 281 (6).

Claims (51)

Compounds of general formula I:

Wherein Q ¹ , Q ² and Q ³ are independently of one another halogen, cyano, nitro, azide, optionally substituted C _1-6 alkyl, optionally substituted C _3-6 cycloalkyl, Optionally substituted C ₃ -containing at least one heteroatom selected from sulfur, oxygen or NR ⁰ , wherein R ⁰ is hydrogen or optionally substituted C _1-6 alkyl. ₆ -heterocyclic group, optionally substituted C _3-6 cycloalkyl (C _1-4 ) alkyl, optionally substituted C _2-6 alkenyl, optionally substituted C _2-6 alkynyl, optionally Substituted C _1-6 alkoxy, optionally substituted C _2-6 alkenyloxy, optionally substituted C _2-6 alkynyloxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted aryl (C _1-6) alkyl, optionally substituted aryl (C _1-6) alkoxy, optionally substituted heteroaryl, optionally substituted heteroaryloxy, heteroaryl (C _1-6), optionally substituted alkyl, optionally substituted heteroaryl (C _{1 -6)} alkoxy, -SF _5, or -S (O) _u (C _1-6) alkyl (wherein, u is 0, 1 or 2, and alkyl groups are optionally substituted by halogen. Or Q ¹ , Q ² and Q ³ are, independently of one another, —OSO ₂ (C _1-4 ) alkyl, wherein the alkyl group is optionally substituted with halogen. Or Q ¹ , Q ^2, and Q ³ are independently of each other, —CONR ^U R ^V , —COR ^U , —CO ₂ R ^U , —CR ^U = NR ^V , —NR ^U R ^V , —NR ^U COR ^V , -NR ^U CO ₂ R ^V , -SO ₂ NR ^U R ^V or -NR ^U SO ₂ R ^W where R ^W is optionally substituted C _1-6 alkyl, and R ^U and R ^V , independently of one another, are C _1-6 optionally substituted with hydrogen or halogen. In the case of alkyl or —CONR ^U R ^V or —SO ₂ NR ^U R ^V , R ^U R ^V is bonded to a 5- or 6-membered carbocycle, or sulfur, oxygen and NR ⁰ (formula In which R ⁰ is hydrogen or optionally substituted C _1-6 alkyl.) May form a heterocycle containing a heteroatom selected from: or when —CR ^U ═NR ^V , R ^V Is hydroxy or optionally substituted C _1-6 alkoxy, optionally substituted aryloxy or optionally substituted heteroaryloxy. Or Q ¹ and Q ² independently of one another additionally denote hydrogen,
R ¹ is optionally substituted C _1-4 alkyl, optionally substituted C _2-4 alkenyl, optionally substituted C _2-4 alkynyl, or optionally substituted C _3-4 cycloalkyl. Yes,
R ² is hydrogen, C _1-8 alkyl, C _3-4 cycloalkyl, C _2-8 alkenyl, cyano, hydroxy, alkoxy, cyano (C _1-4 ) alkyl, C _1-4 alkoxy (C _1-4 ) Alkyl, C _1-4 alkoxy (C _1-4 ) alkoxy (C _1-4 ) alkyl, or benzyloxy (C _1-4 ) alkyl, wherein the phenyl ring is optionally substituted by C _1-4 alkoxy Has been replaced,
R ³ is — (CR ^a R ^b ) _p (CR ^c R ^d ) _q (X) _r (CR ^e R ^f ) _s R ⁴ , where R ^a , R ^b , R ^c , R ^d , R ^e and R ^f , independently of one another, are hydrogen, C _1-4 alkyl, halogen, cyano, hydroxy, C _1-4 alkoxy, or C _1-4 alkoxycarbonyl, or R ^a R ^b , R ^c R ^d or R ^e R ^f may be combined to form a 3-8 membered carbocyclic ring, or sulfur, oxygen and NR ⁰ , where R ⁰ is hydrogen or optionally substituted C _1-6 alkyl. A heterocyclic ring containing a heteroatom selected from
X is (CO), (CO) O, O (CO), O, S (O) _t , where t is 0, 1 or 2, or X is NH or N (C _1-6 ) is alkyl,
p, r and s are independently of each other 0 or 1,
q is 0, 1 or 2;
R ⁴ is optionally substituted C _1-6 alkyl, optionally substituted C _2-6 alkenyl, —CR ^UU ═NR ^VV , where R ^uu is hydrogen or C _1-6 alkyl; And R ^VV is hydroxy or optionally substituted C _1-6 alkoxy, optionally substituted aryloxy or optionally substituted heteroaryloxy), or —CH ₂ —C≡C—R ^5. And where
R ⁵ is hydrogen, halogen, hydroxy, C _1-6 alkoxy, C _1-3 alkoxy (C _1-3 ) alkoxy, cyano, C _1-4 alkylcarbonyloxy, aminocarbonyloxy, mono- or di (C _1-4 ) -alkylaminocarbonyloxy, tri (C _1-4 ) alkylsilyloxy, or —S (O) _g (C _1-6 ) alkyl (wherein g is 0, 1 or 2) . present) by either a C _1-8 alkyl optionally substituted, or R ⁵ is halogen, hydroxy, C _1-6 alkoxy, C _1-3 alkoxy - (C _1-3) alkoxy, cyano, C _1-4 alkylcarbonyloxy, aminocarbonyloxy, mono- or di (C _1-4 ) alkyl-aminocarbonyloxy, tri (C _1-4 ) alkylsilyloxy, or —S (O) _g (C _1-6 ) Alkyl (wherein g is 0) 1 or 2.) By either a C _3-6 cycloalkyl optionally substituted, or R ^5, C _3-6 cycloalkyl (C _1-4) alkyl, wherein alkyl and / or Cycloalkyl moieties may be halogen, hydroxy, C _1-6 alkoxy, C _1-3 alkoxy (C _1-3 ) alkoxy, cyano, C _1-4 alkylcarbonyloxy, aminocarbonyloxy, mono- or di (C _{1- 4} ) Optional by alkylaminocarbonyloxy, tri (C _1-4 ) alkyl-silyloxy, or —S (O) _g (C _1-6 ) alkyl (wherein g is 0, 1 or 2). Or R ⁵ is optionally substituted aryl, optionally substituted aryl (C _1-4 ) alkyl, optionally substituted aryloxy (C _1-4 ) alkyl, optionally substituted Hetero Is aryl, or optionally substituted heteroaryl (C _1-4 ) alkyl, or optionally substituted heteroaryloxy (C _1-4 ) alkyl, or R ⁴ is optionally substituted C _{3 -6} cycloalkyl, optionally substituted C _5-6 cycloalkenyl, optionally substituted aryl, optionally substituted heteroaryl, or sulfur, oxygen or NR ^{0 where} R ⁰ is hydrogen or optional . have been C _1-6 alkyl substituted) or a 5-～8- membered rings that are optionally substituted, optionally containing a heteroatom chosen from, or R ^3, - (CR ^a R ^b ) _P (CR ^c R ^d ) _q (X) _r (CR ^e R ^f ) _s R ⁴ , R ² and R ³ are combined to form halogen, C _1-4 alkyl, mono- or di- Optionally substituted by (C _1-4 ) alkylaminocarbonyl And sulfur, oxygen and NR ^{00 where} R ⁰⁰ is C _1-4 alkyl optionally substituted with halogen, C _1-6 alkoxy or cyano, or R ⁰⁰ is nitro, C _1-4 It is phenyl optionally substituted by alkyl, halo (C _1-4 ) -alkyl, C _1-4 alkylcarbonyl or heteroaryl. A 5- or 6-membered ring optionally containing a heteroatom selected from: or R ² and R ³ are joined to form an optionally substituted 6,6-membered bicycle You can,
R ³ is — (CR ³⁰ R ⁴⁰ ) C≡CR ⁵⁰ , wherein R ³⁰ and R ⁴⁰ are independently of each other hydrogen, C _1-6 alkyl, halo (C _1-4 ) alkyl, C _1-4 alkoxy (C _1-3 ) alkyl, C _2-3 alkenyl, or C _2-3 alkynyl, or R ³⁰ and R ⁴⁰ are attached to the carbon atom to which they are attached; Forming a six-membered carbocycle or a heterocycle containing a heteroatom selected from sulfur, oxygen or NR ⁰⁰⁰ , wherein R ⁰⁰⁰ is hydrogen or C _1-4 alkyl, wherein the carbocycle Or the heterocycle is optionally substituted with halo or C _1-4 alkyl;
R ⁵⁰ is hydrogen, optionally substituted C _1-4 alkyl, optionally substituted C _3-6 cycloalkyl, optionally substituted aryl, or sulfur, oxygen or NR ⁰⁰⁰ (where R ⁰⁰⁰ is Optionally substituted heteroaryl containing a heteroatom selected from: hydrogen or C _1-6 alkyl;
L is sulfur or oxygen, and n is 0, 1 or 2. And salts and N-oxides of compounds of formula I. Q ² is hydrogen, the Q ¹ and Q ^3, are those according to claim 1, a compound according to claim 1. ^2. A compound according to claim 1, wherein Q < ¹ > is halogen, aryl or heteroaryl, Q < ² > is hydrogen, and Q < ³ > is as defined in claim 1. The compound of claim 1, wherein Q ¹ is aryl, Q ² is hydrogen, and Q ³ is as defined in claim 1. ^2. The compound of claim 1, wherein Q < ¹ > is heteroaryl, Q < ² > is hydrogen, and Q < ³ > is that of claim 1. The compound of claim 1, wherein Q ¹ and Q ³ are halogen and Q ² is hydrogen. The compound of claim 1, wherein Q ¹ is aryl or heteroaryl, Q ² is hydrogen, and Q ³ is halogen. The compound of claim 1, wherein Q ¹ and Q ² are hydrogen, and Q ³ is halogen or optionally substituted alkyl. ^2. The compound of claim 1, wherein Q < ¹ > is halogen, Q < ² > is hydrogen, and Q < ³ > is optionally substituted alkyl. The compound of claim ^1, wherein Q ¹ and Q ² are halogen and Q ³ is optionally substituted alkyl. The compound according to claim 1, wherein Q ¹ is bromo. The compound of claim 1, wherein Q ¹ is iodo. The compound according to claim 1, wherein Q ¹ is chloro. The compound of claim 1, wherein Q ¹ is fluoro. Q ³ is a halogen compound of claim 1, wherein. The compound according to claim 1, wherein Q ³ is fluorine. The compound of claim 1, wherein Q ¹ is bromo, Q ² is hydrogen, and Q ³ is fluoro. The compound of claim 1, wherein Q ¹ is bromo, Q ² is hydrogen, and Q ³ is chloro. The compound of claim 1, wherein Q ¹ is iodo, Q ² is hydrogen, and Q ³ is fluoro. The compound of claim 1, wherein Q ¹ is iodo, Q ² is hydrogen, and Q ³ is chloro. 2. A compound according to claim 1, wherein Q < ¹ > is hydrogen, halogen, aryl or heteroaryl. The compound according to claim 1, wherein R ¹ is C _1-4 alkyl or halo (C _1-4 ) alkyl. The compound according to claim 1, wherein R ¹ is methyl. 2. A compound according to claim ^{1 wherein} R < ¹ > is ethyl. The compound according to claim 1, wherein R ² is hydrogen or methyl. The compound of claim 1, wherein R ² is hydrogen. The compound according to claim ¹ , wherein Q ¹ , Q ² and Q ³ are halogen. The compound of claim 1, wherein Q ¹ is halogen, Q ² is C _1-4 alkyl, and Q ³ is halogen. Q ¹ is a halogen, Q ² is a C _1-4 alkyl, and Q ³ is chloro, claim 28 A compound according. Q ¹ is a halogen, Q ² is a C _1-4 alkyl, and Q ³ is fluoro, 28. A compound according. The compound of claim 1, wherein Q ¹ is halogen, Q ² is methyl, and Q ³ is halogen. 32. The compound of claim 31, wherein Q < ¹ > is halogen, Q < ² > is methyl, and Q < ³ > is chloro. 32. The compound of claim 31, wherein Q < ¹ > is halogen, Q < ² > is methyl, and Q < ³ > is fluoro. 32. The compound of claim 31, wherein Q < ¹ > is bromo, Q < ² > is methyl, and Q < ³ > is chloro. 32. The compound of claim 31, wherein Q < ¹ > is bromo, Q < ² > is methyl, and Q < ³ > is fluoro. 32. The compound of claim 31, wherein Q < ¹ > is iodo, Q < ² > is methyl, and Q < ³ > is chloro. 32. The compound of claim 31, wherein Q < ¹ > is iodo, Q < ² > is methyl, and Q < ³ > is fluoro. The compound of claim 1 wherein Q ¹ is halogen and Q ² and Q ³ are C _1-4 alkyl. R ³ is tert-butyl, 1-halo-2-methylprop-2-yl, 1,1-dihalo-2-methylprop-2-yl, 1,1,1-trihalo-2-methylprop-2-yl, 1-alkoxy-2-methylprop-2-yl, 1-alkenyloxy-2-methylprop-2-yl, 1-alkynyloxy-2-methylprop-2-yl, 1-cyano-2-methyl-prop-2-yl Yl, 1-alkoxyalkoxy-2-methyl-prop-2-yl, 1-halo-3-methylbut-3-yl, 1,1-dihalo-3-methylbut-3-yl, 1,1,1-trihalo -3-methylbut-3-yl, 1-alkoxy-3-methylbut-3-yl, 1-alkenyloxy-3-methylbut-3-yl, 1-alkynyloxy-3-methylbut-3-yl, 1 Cyano-3-methylbut-3-yl, 2-cyanoprop-2-yl, 2-methoxycarbonylprop-2-yl or 2-methylaminocarbonylprop-2-yl, 1-alkylthio-2-methylprop-2-yl 1-alkylsulfinyl-2-methylprop-2-yl, 1-alkylsulfonyl-2-methylprop-2-yl, 2-cyano-1-alkoxyprop-2-yl, 2-methyl-1-[(E and / Or Z) -hydroxyimino] -prop-2-yl, 2-methyl-1-[(E and / or Z) -alkoxyimino] -prop-2-yl, 2-methyl-1-[(E and / Or Z) -aryloxyimino] -prop-2-yl, 2-methyl-1-[(E and / or Z) -heteroaryloxyimino] -prop-2-yl, 1- Alkoxy-prop-2-yl, 1-halo-prop-2-yl, 3-methyl-but-1-yn-3-yl, 1-alkyl-3-methyl-but-1-yn-3-yl, 4-methyl-pent-2-yn-4-yl, 1-hydroxy-4-methyl-pent-2-in-4-yl, 1-alkoxy-4-methyl-pent-2-yn-4-yl, 1-alkoxyalkoxy-4-methyl-pent-2-yn-4-yl, 1-alkoxyalkoxyalkyl-4-methyl-pent-2-in-4-yl, 1-cyanoalkyl-3-methylbut-3- The compound of claim 1, which is yl, 1-haloalkyl-3-methylbut-3-yl. R ³ is tert-butyl, 1-halo-2-methylprop-2-yl, 1-fluoro-2-methylprop-2-yl, 1-methoxy-2-methylprop-2-yl, 1-ethoxy-2- Methylprop-2-yl, 1-allyloxy-2-methylprop-2-yl, 1- (prop-2-ynyloxy) -2-methylprop-2-yl, 2-cyano-1-ethoxy-prop-2-yl, 2-cyano-1-methoxyprop-2-yl, 1-halo-3-methylbut-3-yl, 1-fluoro-3-methylbut-3-yl, 3-methylbut-1-in-3-yl, 4 -Methylpent-2-yn-4-yl, 5-methyl-hex-3-in-5-yl, 1-methoxy-4-methyl-pent-2-yn-4-yl, 1-allyloxy-4-methyl -Pent- 40. -In-4-yl, 1-propargyloxy-4-methyl-pent-2-yn-4-yl, 1-ethoxy-4-methyl-pent-2-yn-4-yl. Compound. R ⁴ is C _1-6 alkyl optionally substituted by C _1-4 alkoxy- (C _1-4 ) alkoxy (C _1-4 ) alkyl, wherein the alkyl group is halo, mono- or di- C _1- optionally substituted _by- (C _1-6 ) alkylamino or tri (C _1-4 ) alkylsilyl, or R ⁴ optionally substituted by benzyloxy (C _1-4 ) alkyl. ₆ alkyl, wherein the alkyl group is optionally substituted by halo, mono- or di- (C _1-6 ) alkylamino or tri (C _1-4 ) alkylsilyl, or R ⁴ is C _2-6 alkenyloxy or _{-S (O) x (C 1-6} ) C 1-6 alkyl optionally substituted by alkyl, wherein x is 0, 1 or 2, and the alkyl group , halo, mono- - or di - (C _1-6) alkylamino, -N (C _1-4) it is optionally substituted with alkyl = NOR, wherein R is a hydrogen or C _1-4 alkyl, or wherein the alkyl group, the tri (C _1-4) alkylsilyl Optionally substituted or R ⁴ is —CR ^UU ═NR ^VV where R ^UU is hydrogen or C _1-6 alkyl and R ^VV is hydroxy or optionally substituted C _2. A compound according to claim 1 which is _1-6 alkoxy. Optionally substituted aryl and optionally substituted heteroaryl rings or moieties of the meaning R ⁵ are halogen, cyano, nitro, azide, C _1-6 alkyl, halo (C _1-6 ) Alkyl, C _3-6 cycloalkyl, C _3-6 cycloalkyl (C _1-4 ) alkyl, C _2-6 alkenyl, halo (C _2-6 ) alkenyl, C _2-6 alkynyl, halo (C _2-6 ) Alkynyl, C _1-6 alkoxy, halo (C _1-6 ) alkoxy, C _2-6 alkenyloxy, halo (C _2-6 ) alkenyloxy, C _2-6 alkynyloxy, halo (C _2-6 ) alkynyl Oxy, aryl, aryloxy, aryl (C _1-6 ) alkyl, aryl (C _1-6 ) alkoxy, heteroaryl, heteroaryloxy, heteroaryl (C _1-6 ) alkyl, heteroaryl (C _1-6 ) alkoxy, -SF _5, -S (O) _g (C _1-4 ) alkyl optionally substituted, where g is 0, 1 or 2, and alkyl is optionally substituted with halo, or R ⁵ is Optionally substituted with —OSO ₂ (C _1-4 ) alkyl, wherein the alkyl group is optionally substituted with halo, or R ⁵ is —CONR ^g R ^h , —COR ^g , —CO ₂ R ^g , —R ^g = NR ^h , —NR ^g R ^h , —NR ^g COR ^h , —NR ^g CO ₂ R ^h , —SO ₂ NR ^g R ^h , or —NR ^g SO ₂ R ⁱ optionally Substituted, wherein R ⁱ is C _1-6 alkyl optionally substituted with halogen, and R ^g and R ^h , independently of one another, are hydrogen or C optionally substituted with halogen. _1-6 alkyl or —CONR ^g R ^h or —SO ₂ NR ^g R ^h Where R ^g R ^h is bonded to a 5- or 6-membered carbocycle, or sulfur, oxygen or NR ⁰ , where R ⁰ is hydrogen or optionally substituted C _1-6 alkyl. The compound of claim 1, which may form a heterocycle containing a heteroatom selected from: In an optionally substituted aryl, optionally substituted heteroaryl or optionally substituted 5- to 8-membered ring, R ⁴ is halogen, cyano, nitro, azide, C _1-6 alkyl, halo ( C _1-6 ) alkyl, C _3-6 cycloalkyl, C _3-6 cycloalkyl (C _1-4 ) alkyl, C _2-6 alkenyl, halo (C _2-6 ) alkenyl, C _2-6 alkynyl, halo (C _2-6 ) alkynyl, C _1-6 alkoxy, halo (C _1-6 ) alkoxy, C _2-6 alkenyloxy, halo (C _2-6 ) alkenyloxy, C _2-6 alkynyloxy, halo (C _2-6 ) Alkynyloxy, —SF ₅ , —S (O) _x (C _1-6 ) alkyl, optionally substituted, where x is 0, 1 or 2, and the alkyl group is or optionally substituted by halo, or R ^4, -OSO ₂ (C _1-4) alkyl It is optionally substituted with, wherein the alkyl group, ^{halogen, -CONR x R y, -CON (} OR x) R y, -COR x, -CO 2 R x, -CR x = NR y, -NR ^{x R y, -NR x COR y} , -NR x CO 2 R y, which is optionally substituted by -SO ₂ NR ^x R ^y or -NR ^X SO ₂ R ^Z,, wherein R ^z is a halogen a C _1-8 alkyl optionally substituted, and R ^x and R ^y are independently of each other, it is C _1-6 alkyl optionally substituted by hydrogen or halogen, a compound according to claim 1. R ⁵⁰ is halogen, hydroxy, C _1-6 alkoxy, C _2-6 alkenyl, C _2-6 alkynyl, C _1-4 alkoxy (C _1-4 ) alkoxy, cyano, C _1-4 alkylcarbonyloxy, amino Carbonyloxy, mono- or di (C _1-4 ) alkylamino-carbonyloxy, S (O) _p (C _1-6 ) -alkyl (wherein p is 0, 1 or 2), triazolyl , Pyrazolyl, imidazolyl, tri (C _1-4 ) -alkylsilyloxy, optionally substituted phenoxy, optionally substituted thienyloxy, optionally substituted benzyloxy, or optionally substituted thienylmethoxy The compound of claim 1, which is C _1-4 alkyl substituted. R ⁵⁰ is halogen, hydroxy, C _1-6 alkoxy, C _1-4 alkoxy (C _1-4 ) alkoxy, cyano, C _1-4 alkylcarbonyloxy, aminocarbonyloxy, mono- or di (C _1-4 ) Alkylamino-carbonyloxy, S (O) _p (C _1-6 ) -alkyl (wherein p is 0, 1 or 2), triazolyl, pyrazolyl, imidazolyl, tri (C _1-4 ) -Alkylsilyloxy, optionally substituted phenoxy, optionally substituted thienyloxy, optionally substituted benzyloxy, or optionally substituted thienylmethoxy is C _3-6 cycloalkyl. The compound of claim 1. In optionally substituted aryl or optionally substituted heteroaryl, R ⁵⁰ is halogen, hydroxy, mercapto, C _1-4 alkyl, C _2-4 alkenyl, C _2-4 alkynyl, C _1-4 alkoxy, C _2-4 alkenyloxy, C _2-4 alkynyloxy, halo (C _1-4 ) alkyl, halo (C _1-4 ) alkoxy, C _1-4 alkylthio, halo (C _1-4 ) -alkylthio, hydroxy ( C _1-4 ) alkyl, C _1-4 alkoxy (C _1-4 ) alkyl, C _3-6 cycloalkyl, C _3-6 cycloalkyl- (C _1-4 ) alkyl, phenoxy, benzyloxy, benzoyloxy, cyano, isocyano, thiocyanato, isothiocyanato, ^{nitro, NR p R q, NHCOR P} , -NHCONR p R q, CONR p R q, -SO 2 R 0, OSO 2 R 0, COR P, CR p = NR q or = CR ^p R being optionally substituted by ^q, wherein R ⁰ is, C _1-4 alkyl, halo (C _1-4) alkyl, C _1-4 alkoxy, halo (C _1-4) alkoxy, C _1-4 alkylthio, C _3-6 cycloalkyl, C _3-6 cycloalkyl (C _1-4 ) alkyl, phenyl or benzyl, and the phenyl and benzyl groups are halogen, C _1-4 alkyl or C _1. Optionally substituted by _-4 alkoxy, and R ^p and R ^q are independently hydrogen, C _1-4 alkyl, halo (C _1-4 ) alkyl, C _1-4 alkoxy, halo (C _{1 -4} ) alkoxy, C _1-4 alkylthio, C _3-6 cycloalkyl, C _3-6 cycloalkyl (C _1-4 ) alkyl, phenyl or benzyl, the phenyl group and benzyl group being halogen, C ₁ optionally substituted by _-4 alkyl or C _1-4 alkoxy,請The compound of claim 1.   The compound of claim 1, wherein L is oxygen.   The compound according to claim 1, wherein n is 0.   A process for the preparation of a compound of formula I according to claim 1 as described herein.   A fungicidal composition comprising a fungicidally effective amount of a compound according to claim 1 and a carrier or diluent suitable therefor.   Applying a fungicidally effective amount of the compound according to claim 1 to the plant, to the seed of the plant, to the plant or the place of growth of the seed, or to the soil or to any other plant growth medium. , A method for controlling or controlling phytopathogenic fungi.